than. ROV. 1993. 9s.

145-172 145

Unimolecular Photochemistry of Anthracenes

COflttWltS
I. IntmdUctlon 145
11. Electron Spectral RoparUes of Anthracenes 146
111. Photochemlsby of Nonplanar Anthracenes 147
IV. Photolytic Transformatbns of AnUuacenes 149
V. Intramolecular Energy Transfer in Substituted 151
Anthracenes
A. photophyalcal Effects 151
E. Isomerlzatlom, InvoMng Energy Transfer 153
VI. Chemlcal Consequences of Intrarolecular 153
Electron Transfer
VII. Excited-State Reactlona of AnthryLSubstmned 154
Alkenes. Azomethlnes. and Azines
A. Geometrical Isomerlzatlon and 154
Cycloaddition Reaclbns Hans-Diater Becker was ban In Qemmny in 1931. He SMied
E. Dehydrocyclizatlons 157 chemistryfrom 195110 1959attheUniversltyofCiimkr(len,where
VIII. lmerization of NonConjugathrely Llnked 157 he dM his doctoral research under lhe direction of G. 0. Schenck
Blchromophorlc Anthracenes on b e n z ~ s M z e phdochmlcal
d autoxldntlonsof organic
compounds. ARer postdoctoral studies at Chalmers University of
A. Anthracenophanes and Anthracene Crow 158 TechnologyinGolhenburg.Sweden (1959-1960),meUniversityof
Ethers Wisconsin in Madison (1960-1961), and Iowa State Unlversity In
E. Dhnthrylalkanes and Theh Derivatives 159 Ames (1961-1962). he joined the General Electrlc Research
Laboratory in Schenectady. New York. in 1963. He lefl GE in 1970
C. DimethylsllyKinked BIchr~nophorIc 162 lo assume a research position at the Department of Organic
Anthracenes Chemislry at Chalmers University of Technologyand lbUniversity
D. Anlhryhlkyl Ethers 162 of Gothenburg. His experimental engagement during the past 15
IX. Retrospective Comemplatlons and Conclusions 164 years In lhe synthesis. slructural studies. and photochemislry of
chromophorically substituted anthracenes has been summarized
X. References 165 recently in a conhibution to me Advances in Fiwtochemlsby. His
previous investigations have dean with photochemical react!
invoivlng phenols, the oxidation of phenols and phenolic benzyl
I. Introduction alcohols. quinone dehydrogenations. and photochemical Isomer-
lkatbns of spirwpxy-substltuted 2,4-cyclohexadenones.and their
Duringthecourseofhiastudiesonsolidhydrocarbons various Did-Alder products.
that were obtainable from coal tar by distillation, J.
Fritzache discovered in 1866 that saturated solutions gated, mainly in order to establish the scope of the
of anthracene (1) upon exposure to sunlight gave a dimerization. Also, research was focused on the struc-
colorless crystalline precipitate which regenerated ture and stereochemistry of the photoproducta, which
anthracene upon melting.1.2 The dimeric nature of the were generally found to be derived by head-to-tail 4s
+ 4s cycloaddition involving the central ring of the
anthracene r-system.*0-36
2 m hr - X The essentials of anthracene photochemistry as seen
by 1963/1964were the subject of a contribution to the
firat volume of the Aduances in Photochemistry and
t 2 were discussed in a review of photochemical reactions
or organic molecule^.^^ A large number of subsequent
photoproduct was established in 1891 by molecular detailed studies on the mechanism of dimerization, and
weight determination, and the correct structure was on the deactivation of photoexcited anthracenes by
proposed before the turn of the Mechanism fluorescence and phosphorescence then provided fun-
studies on the photochemicalformationof dianthracene damentally important r e ~ u l t s ,which
3 ~ ~ were
~ reviewed
(2) commenced as early as 1905.6 In particular, the in a textbook on organic photochemistry published in
photophysical aspects and the reversibility of the 1976.% By that time, much of our present-day knowl-
reaction were studied during the following50 years.7-19 edge about intramolecular energy-transfer processes
Between 1955 and 1965,concomitant with the re- had been gained by investigating bichromophoric
newed interest in organic photochemistry, many of the compounds in which the anthracene chromophore was
easily available substituted anthracenes were investi- one of the two interacting s-sy~tems.~-~~ Moreover,
0009-2665/93/07936145$12.M)/0 @ 1993 Amnican chemical Sociay
146 Chemlcal Reviews, 1993, Vol. 93, No. 1

the photochemistry of anthracene derivatives, in con- (SI)is 76 kcdmol. The energy level of the lowest triplet
junction with elegant ground-state reactions, had state (TI)is 42 kcal/mol above that of SO.Significantly,
enriched organic chemistry with some remarkable novel the second triplet state (Tz)of anthracene lies 74 kcal/
structures, namely, 9,lO-dehydrodianthracene(31, 9,- mol above SO,i.e. 2 kcal/mol below SI,and intersystem
ltY-dehydrodianthracene (4), 9,Ydidehydrodianthracene crossing from the SI state to the triplet state proceeds
(5), and 9,Y,10,10'-tetradehydrodianthracene (6hBtmZ efficiently with a quantum yield of 0.7. The quantum
yield of fluorescence is 0.3, and it has been established
for numerous substituted anthracenes that the sum of
quantum yields of fluorescence and of intersystem
crossing to the triplet state typically is unity. Thus,
for many anthracene derivatives, deactivation of the SI
state by internal conversion is negligibleqMg
3 4 The effects of substituenta on the electronic absorp
tion and emission spectra of anthracenes have been of
longstanding interest, and the fluorescence properties

x
of substituted anthracenes have been studied in
det~d.'~+'l Substitution of the anthracene chromophore
lowers the SIenergy level, thus changing the excited-
state properties by affecting the energy gap between
the SI and TZstates and, consequently, the quantum
yield of intersystem crossing. By the same token, the
5 6 quantum yields of fluorescence at room temperature
vary greatly for the multitude of known anthracene
The present review deals with unimolecular photo- derivatives. For example, 9,lO-diphenylethynyl-sub-
chemical reactions of anthracene derivatives, including stituted anthracene fluoresces with a quantum yield of
intramolecular reactions of bichromophoric anthracenes, about unity, while the quantum yield of fluorescence
most of which were studied during the past 20 years. for 9-bromoanthracene, in which the halogen may
The limitation of the scope of the review by excluding enhance the rate of intersystem crossing, is about
bimolecular photochemistry was deemed mandatory 0.01.769829899-Carbonyl-substituted anthracene deriv-
in view of the overwhelming number of articles dealing atives, in general, are nonfluorescent due to efficient
with addition reactions, and with the photophysical population of the triplet state.g2 For a variety of
consequences of bimolecular interactions. For several substituted anthracenes, such as 9-anthramide, inter-
topics involvingelectronicallyexcited anthracenes, such action with polar solvents will alter the nature of the
as the formation of intramolecular exciplexes, twisted lowest excited state, as can be evidenced from the
intramolecular charge transfer (TICT)states, adiabatic marked solvent dependence of the fluorescence spec-
cycloreversions, and rotational isomerism in anthryl- trum, and in solvent dependent In
substituted ethylenes, comprehensivereviews have been some cases, such as that of 9-tert-butylanthracene
published previously.B3* Likewise, the role of an- discussed in section 111, the low fluorescence quantum
thracene derivatives in photochromic systems has been yield (0.011) is associated with the deactivation of the
treated elsewhere.67 S1 state by both internal conversion and intramolecular
chemical reaction, rather than with intersystem crossing
I I . Electron Spectral Propertles of Anthracenes to the triplet state.82 The fluorescence quenching of
The electronic absorption and emission spectra of anthracene by carbon tetrachloride is due to intermo-
anthracene are being described in detail in most lecular reaction of photoexcited anthracene with the
solvent.424477S
textbooks and monographs on photochemistry and
spectroscopy.6g72Therefore, this section will be limited The relationship between molecular geometry and
to a brief outline of only those spectroscopic features electron spectral properties has been investigated both
which are of direct relevance to the unimolecular experimentally and theoretically. Of particular interest
photochemistry of anthracenes. are A-chromophorically substituted anthracenes, such
For anthracene, the electronic absorption of photo- as 9-phenylanthracene, in which coplanarity of the two
chemical interest is characterized by a series of vibra- A-systems,i.e. conjugation in the electronicground state,
tionally spaced bands around 350 nm. The longest is precluded for steric reasons.@* In general, the shape
wavelength transition near 380 nm has an extinction of of the fluorescence spectrum and the shape of the
about 9 OOO M-' cm-'. The short wavelength absorption absorption spectrum are characterized by a mirror-
around 254 nm, having an extinction of about 200 OOO image relationship, and Stokesshiftstypically are about
M-' cm-l, is hardly ever utilized in photochemical 150 cm-', if the differences between the geometry of
context for practical reasons, since electronicexcitation the electronic ground state SOand the emitting excited
of the photoproducts, generally absorbing light in this state SIare small. Large Stokes shifts of up to 10 O00
region of the spectrum,is undesirable. It is worth noting cm-l, indicative of large differences between the ge-
that irradiation of solutions of anthracene in cyclo- ometry of the SOstate and that of the SI state, have
hexane with unfiltered light from a mercury lamp does been found to characterize the luminescence of various
not give dianthracene, as had been claimed,73but yields 9-anthrylethylene derivatives and 1,2-di9-anthryleth-
a degradation product of unknown structure.39 ylenes, which cannot assume a planar ground-state
The energy difference between the electronic ground geometry for steric Moreover, topolog-
state (So)of anthracene and ita first excited singlet state ically facilitated intramolecular charge-transfer inter-
Unimolecular Photochemistry of Anthracenes Chemlcal Reviews, 1993, Vd. 93,No. 1 147

actions between a photoexcited anthracene 7-system

and an electron donor or acceptor moiety may give rise
to an exciplex which is characterized by red-shifted 12 13
structureless e m i s ~ i o n . ~ ~For
J l ~ example, the an-
thracene derivative 9 in cyclohexane solution is char- isomerization of anthracene, although both have been
acterized by a structured fluorescence spectrum (@F = prepared by multistep s y n t h e ~ e s . ~Dewar ~ J ~ ~isomers
0.84) around 425 nm, while its electronically excited 12 and 13 revert to anthracene in a thermal reaction
rotamer 8,generated by photolytic cycloreversion of 7, which is associated with an activation barrier of 21.6
gives rise to a broad structureless exciplex emission (@F and 26.5 kcal/mol, respectively. For the 1,4-Dewar
0.8) around 600 nm.ll1-ll5 isomer 13,it has been established that the photolytic
electrocyclic ring opening, proceeding with a quantum
yield of 0.41, in part affords electronically excited
anthracene (@ -0.1) in an adiabatic cyclore~ersion.~~~
The photolytic aromatization of 1,4-Dewa1naphthalene
also proceeds a d i a b a t i ~ a l l y . l ~ ~ - l ~
Decamethylanthracene (141,for which an X-ray
diffraction analysis indicates the lateral benzene rings
7 8 B to assume boat conformations, smoothly yields the
Dewar isomer 15 by direct irradiation at room tem-
The chromophoric and fluorophoric properties of perature with Pyrex-filtered light in degassed solu-
anthracene derivatives have long been of practical tion.'& Dewar anthracene 15 has been isolated and
interest in analytical context, and numerouschemically C H 3 @CH3
y H 3CH3 CH3 C CH3
H CH33 CH3 M
reactive anthracene derivatives, such as isocyanates or
acid chlorides, are being utilized as labeling agents for
the detection and estimation of UV transparent
CH3
/ / /

CH3 CH3 CH3

CH3
- A CH3
CH3 CHI CH3
CH3

substrates.11B-121However, most recent interest in the 14 15

fluorescence properties of substituted anthracenes
derives from their application as probes and chemo- characterized, and ita thermal reversion to 14 has been
sensor^.^^^-^^ Numerous examples of anthracene de- established. However, as is typical of sterically crowded
rivatives, particularly anthryl-substituted crown ethers 9-methylanthracenes, decamethylanthracene also is
and cryptands, whose fluorescence properties may be prone to isomerize by 1,5-hydrogen migration in a
drastically affected by the environment, have been reaction which is catalyzed by traces of The
investigated in recent years. Complexation by metal analogous isomerization of 6-methylpentacene(16)into
ions, or protonation, typically will enhance the fluo- 17 has been reported to be a photochemical reacti011.l~~
rescence quantum yield, as fluorescence quenching due
to intramolecular electron transfer will no longer be
operative. Thus, for 9,lO-diaminoalkyl-substituted
anthracene 10,chelation with zinc chloride leading to
the binuclear complex 11 was found to enhance the 18 17
intensity of fluorescence by a factor of about 1000.128
9-Methoxyoctamethylanthracene18a as well as 9,-
10-dialkoxyoctamethylanthracenes 18b-d are seem-
ingly photostable at room temperature. Upon irradi-
ation at -78 OC, however, anthracenes 18a-d are found
to react smoothly, giving the corresponding Dewar
isomers 19,whose structures were deduced from NMR
and electron spectral data. Dewar anthracenes 19were
not isolable, as they reverted to their anthracene isomers
above -30 OC.150
CH3 R' CH3 CH3 R' CH3
3 J hv
C H 3 @ $ c H3H p@ . ' "

The cation-sensitive fluorescence properties of bisan- C H ~

.
'''
CH3 R2 CH3
C H -78'c
~ CH3
CH3 R2 CH3
CH3
thraceno crown ethers and cryptands have been studied
in detail in conjunction with their photochemistry (cf. 18 -
a: R' methoxy; R2= H 18

--
section VIII.A), and the subject has been reviewed b: R' = I? = methoxy
C: R' R2 ethoxy
re~ent1y.l~~ d: R'
I

R2 -isopropoxy

I I I . Photochemhtry of Nonplanar Anthracenes Significantly,irradiation of octamethylanthracene 20

at -78 OC did not yield any Dewar isomer but produced
Sterically demanding substituents, which cause the a radical species, suggested to have structure 21,from
ground-state geometry of aromatic hydrocarbons to which octamethylanthracene 20 was regenerated above
deviate from planarity, generally are a prerequisite for -30 OC.150
photochemical valence isomerizations. Therefore, nei- Neither 1,5,9,10-tetramethylanthracene(22)nor 1,8,9,-
ther 9,lO-Dewar anthracene (12) nor 1,4-Dewar an- 10-tetramethylanthracene (23)isomerize upon irradi-
thracene (13)are accessible by direct photochemical ation, although their facile autoxidation under ambient
148 Chemical Reviews, 1993, Vol. 93, No. 1

the excited singlet state to ground state appears to be

the main mode of deactivation. In viscous solvents,
the observed double-exponential fluorescencedecay has
been attributed to the involvement of an undefined
intermediate precursor of 9-tert-butyl-9,10-(Dewar an-
thracene).
Photoexcitation of 9-tert-butyl-9,10-(Dewar an-
thracene) results in cycloreversionwith a quantum yield
of 0.35.1sJ67 The activation energy associated with the
thermal regeneration of 9-tert-butylanthracene from
conditions leading to endoperoxides indicates that the 26 is 22.3 kcal/mol.'%
anthracene *-system is geometrically distorted.160Sim- The only other geometrically distorted anthracene
ilar easy autoxidation characterizes various (9,lO)- thus far found to be photochemically convertible (a =
anthracenophanes in which the anthracene *-system 0.016) into its Dewar isomer is 9-tert-pentylanthracene
severely deviates from ~ l a n a r i t y . ' ~ ~ J ~ ~ (%= 0.008).157J58Unexpectedly, irradiation of 9-tert-
Remarkably, 9-methoxyanthracenehas recently been butyl-10-cyanoanthracene (27) in acetonitrile at 0 O C
does not give the corresponding Dewar anthracene but

@m&
suggested to isomerize photochemically to give 9-meth-
oxy(Dewar anthracene) (24), since it had been found yields the isomeric dibenzonorbornadiene derivative
28, whose formation involves the skeletalrearrangement
CH3 CH3 CHI
FH3

0 0 0 / 0 /

CH3 CH3 CH3

P 23 24

that 9-methoxyanthracene in solution disappears upon n 28

photoexcitation, and the reaction turned out to be
thermally reversible.'53 The photochemical formation of the tert-butyl group.162A t room temperature, 9-tert-
of g-methoxy(Dewar anthracene) would be unique butyl-10-cyanoanthracenein fluid solution is virtually
insofar as the anthracene *-system in 9-methoxyan- nonfluorescent (a < 0.001), and investigation of pho-
thracene is virtually planar, the folding angle about the toexcited 27 between 77 K and 163 K in a poly(methy1
9,lO axis being only 178.6'. It appears to be more methacrylate) matrix by single-photon counting indi-
reasonable to assume that the spectroscopically de- cates multiexponential decay.163
tected reversible process is attributable to the photo- The photochemistry of 9-(trifluoromethyl)anthracene
chemical formation of a thermally labile head-to-head has been studied, and it was found to dimerize by 4%
dimer of 9-methoxyanthracene, which in solution at + 4?r cycloaddition upon irradiation at 0 OC,even at
room temperature dissociates to regenerate 9-meth- low concentration (<1VM). The head-btail structure
oxyanthracene. The formation of a head-to-tail dimer of the dimer was established by X-ray diffraction
(35% yield) by irradiation of 9-methoxyanthracene analysis.la Neither 9-(dimethylphenylsily1)anthracene
(N M) in ether solution has been reported earlier.28 (@F = 0.86) nor 9-(trimethylsilyl)anthracene (@F = 0.79)
Most detailed and quantitative data are available on led to Dewar isomers upon irradiation at low concen-
the thermally reversible photochemical conversion of tration in hydrocarbon solvents.lS A t high concen-
9-tert-butylanthracene (25) into 9-tert-butyl-9,lO- tration in non-polar solvents, g-trimethylsilylan-
(Dewar anthracene) (26).'"-" Moreover,the structures thracene does undergo dimerization by 4a + 41r
of both isomers in question have been analyzed by X-ray cyc10addition.l~~
diffraction." Thus, the aromatic *-system in 9-tert- A most remarkable photochemical reaction has been
butylanthracene deviates from planarity by a folding observed for [lo] (9,10)anthracenopha-4,6-diyne(29)
angle of 166.2' about the molecular short axis. In the which upon exposure to sunlight is smoothly converted
[2.2.0lbicyclohexadiene moiety of the Dewar isomer into the radialene derivative 31.'& A spectroscopic
26, the dihedral angle about the photochemically formed investigation has revealed that the photochemical step
bond (1.623 A) is 113'. involves singlet state isomerization of 29 to the strained
cumulene 30, which dimerizes to give 31 in a thermal
FH3
H&-C-CHa
943
HsC-C-CH3
rea~ti0n.l~'

& % &A
25 26

Unique photochemical properties of 9-tert-butylan-

thracene are indicated by ita exceptionally low fluo-
rescence quantum yield at room temperature and by 2s 30 v 3 1 "
negligible intersystem crossing to the triplet state. The
photochemical isomerization of 9-tert-butylanthracene Recently, [6] (1,4)anthracenophane (34) has been
in dilute solution intothe Dewar anthracene 26 proceeds synthesized, and its bent molecular geometry has been
with a quantum yield of about 0.016. Thus, at room established by X-ray diffraction." Different from [61-
temperature in fluid solution, internal donversion from paracyclophane (32) and [6](1,4)naphthalenophane
Unlmolecular Photochemistry of Anthracenes Chemical Reviews, 1993, Vol. 93,No. 1 148

(33), which are photochemically converted into the For substituted anthracenes, the course of their
correspondingDewar isomers, anthracenophane 34 does intramolecular photolytic transformations is governed
not isomerize photochemically but yields dimeric by the nature of the substituent and by their excited-
+
products by 2u 2a cycloaddition involving the 1,2 state interactions with the anthracene *-system. The
b ~ n d . ' ~ * lThe
~ ~ photochemical dimerization of 34 is examples of unimolecular photochemistry thus are
suggested to proceed via an excited triplet state.16gIt limited to those anthracene derivatives in which the
is worth noting that the 1,2 bond in anthracenophane substituent typically is characterized by lone-pair
34 also is highly reactive in ground-state reactions with electrons. Frequently, primary products of unimolec-
ele~trophiles.'~~J~~ ular photochemical reactions of anthracenes are un-
stable and may react further, particularly by oxidation

~ H Z
7th
0
CHz-CHz

CHp-CHz
CHp-CHz

iH2
FH2
@
CHz-CHz
0 0
CHz-CHz

@
'
~ H P
FHz
CHz-CHz
or dimerization. For example, the photochemistry of
9-hydroxyanthracene (39) is complicated not only
because of the solvent-dependent ground-state equi-
librium with anthrone (40), but also by the facile
32 33 34
&
\ 0L0 &
7

Various geometrically distorted 9,lO-anthraquinone H H

derivatives have been synthesized in recent years, and 38 40

their photochemical isomerization has been investi-

gated. Thus, [6]-1,4-cyclophaneanthraquinone(35) formation of various autoxidation p r o d u ~ t s . ~ The
~~-'~~
upon irradiation in deuteriochloroform or methylcy- photochemical tautomerization of 9-anthrone to give
clohexanesolution, using light of wavelengths >400nm, 9-hydroxyanthracene, in turn, is complicated by the
unfavorable electron spectral differences between the
smoothly yields the Dewar isomer 36, which is char- two isomers and by inadvertent intermolecular hydro-
acterized by a half-life of 10min at 80 0C.174Analogous gen atom abstraction reactions by the photoexcited
Dewar isomers were formed (a = 0.03) by irradiation anthrone.182 Laser flash investigations have revealed
of 1,2,3-tri-tert-butyl- and 1,2-di-tert-butyl-3-(tri- that triplet-excited 9-hydroxanthraceneis formed from
methylsily1)anthraquinone. An apparent prerequisite triplet-excited 9-anthrone by way of bimolecular energy
for the valence isomerization of anthraquinone deriv- transfer." Although the triplet energy of 9-anthrone
atives is the xu* nature of the excited state involved (71.5 kcal/mol) is considerably higher than that of
~ ~the lowest excited state of tert-
in the r e a ~ t i 0 n . l If 9-hydroxyanthracene (about 43 kcal/mol), direct pop-
butyl-substituted anthraquinones is n?r*in nature, their ulation of the triplet state of 9-hydroxyanthracene by
unimolecular photochemistry will be characterized by excitation of 9-anthrone has not been observed in
intramolecular hydrogen atom transfer reactions. picosecond laser experiments.'@
Considerable efforts have been devoted to investi-
gating the photochemistry of 9-nitroanthracene
(41).'*la The virtual lack of 9-nitroanthracene flu-

&L&
41 42

I V. Photo&tlc Transtormations of Anthracenes

orescence is indicative of efficient intersystem crossing
from the lowest excited uu* singlet state to an upper
Unimolecular transformations of unsubstituted an- nu* triplet ~ t a t e . ' ~The ~J~ weak luminescence with
thracene have not been reported yet. However, the maxima around 685 and 760 nm observed at 77 K in
photolysis of anthracenein very dilute aqueous solution a solid matrix has been attributed to 9-nitroanthracene
(3 X lo-" M, argon purged; X 350 nm) has recently been phosphorescence.189Jw However, luminescence ob-
found to give as main products three stereoisomers of served in solid matrices also can arise from various
lO,lO'-dihydroxy-9,9', lO,lO'-tetrahydro-9,9'-bianthryl photoproducts of 9-nitroanthracene, particularly 9,lO-
(38). The result has been rationalized by the inter- anthraquinone, which may be formed from photoexcited
mediacy of the anthracene cation radical, followed by 9-nitroanthracene with high quantum efficiency (0.7)
reaction with water, and dimerization of radical 37.176 due to the presence of oxygen.192Jg3 A holographic study
has revealed that 9-nitroanthracene in a polymer matrix
disappears upon irradiation at 458 nm to give 9-hy-
droxyanthracene (39)with a quantum yield of about
0.01."
Evidence for the photolytic decomposition of 9-ni-
troanthracene was obtained in an early investigation
in which irradiation with light of wavelengths of 370-
410 nm was found to give nitric oxide and 10,lO'-
bianthronyl(44), while excitation at longer wavelengths
(420-530 nm) yielded the 4u + 4u head-to-tail cy-
37 38 clodimer of 9 - n i t r o a n t h r a ~ e n e . ~In
~ Ja~ subsequent
150 Chemical Reviews, 1993, Vol. 93,No. 1

detailed preparative study, the intramolecular reaction the carbonyl substituent become feasible." In fluid
of an upper n7r* triplet state of nitroanthracene was solution, 9-anthryl ketones typically are nonfluorescent
suggested to lead to 9-anthryl nitrite (42) via an because of efficient intersystem crossing to the triplet
oxaziridine intermediate.'= The observed formation state.92 Picosecond laser experiments indicate that
of 44 was accounted for by cleavage of 9-anthryl nitrite deactivation of the excited singlet state (a**) of
leading to nitric oxide and 9-anthryloxy radical 43, 9-anthryl ketones to the lowest excited triplet state
which can dimerize or give anthraquinone monoxime (TIT**) involves very fast intersystem crossing from
via a radical recombination process. S1mr* to an upper triplet state with n7r* character.200
Within the group of carbonyl-substituted anthracenes,
9-anthryl a-bromoalkyl ketones are unique insofar as
the a-bromoalkyl ketone moiety is characterized by a
photochemically labile carbon-halogen bond. Thus,
\ / \ / the unimolecular photochemistry of both 9-(w-bro-
43 U
moacety1)anthracene (49a) and 9-(cr-bromopropionyl)-
anthracene (49b) involves cleavage of the carbon-
In a series of spectroscopic investigations on 9-ni- bromine bond. Photoexcited 49a isomerizesmainly by
troanthracene, 9-benzoyl-lO-nitroanthracene, and 9-cy- carbon-halogen addition to the 1,2-bond to give the
ano-10-nitroanthracene, the photochemical formation labile primary product 50a, from which hydrogen
of 9-anthryloxy radicals as primary products has been bromide is eliminated either photochemically or ther-
confirmed, including by electron-spin resonance spectra. mally. Byproducts formed in the photolysis of (bro-
Moreover, the kinetics of pico- and nanosecond spec- moacety1)anthracene 49a are 9-bromoanthracene,
troscopic experiments indicate that, followingexcitation 9-acetylanthracene, and anthracene. In the case of 9-(a-
to the Sl(m*) singlet state, the lowest excited triplet bromopropionyl)anthracene,the main photoproducts
state (Tl(7r**) is populated via the internal conversion isolated were 2-methyl-1-aceanthrenone (51b;43 %) and
of T,(ns*) .187J91 9-anthryl vinyl ketone (52,42 % ). At -196 "C, irradi-
In terms of unimolecular phochemistry, the excited- ation of 49b leads exclusively to 52, suggesting that
state properties of sodium 9-anthracenecarboxylate (45) changesin the molecular geometry of 49b are important
resemble those of 9-nitroanthracene insofar as 10,lO'- for the formation of the intermediate 50b.
bianthronyl(44), as well as anthracene, can be formed
as byproducts, depending on reaction conditions.lg5
Dimerization by 47r + 47r cycloaddition generally is the
predominant photochemical reaction of sodium 9-an-
thra~enecarboxylate.~~ Irradiation in degassed solution
has been found to give carbon monoxide and the anion
of 9-hydroxyanthracene (47)whose formation has been
Na' -O.c.o 0-c-o- 4a

&y&-& 0 0 0 0 0 0
-
a:R-H
b: R CH3
52
45 4a 47
Unequivocal evidence for the involvement of radicals
rationalized by the intermediacy of 46.Ig5 has been obtained in the photolysis of a-(9-anthryloxy)-
9-(Trimethylsily1)anthracene(48) has been found to acetophenone (531, which was found to disappear with
undergo smooth photolytic protodesilylation in meth- a quantum yield of 0.24 upon irradiation in methanol
anol solution,yielding anthracene with a quantum yield solution.2MThe CIDNP spectrum in acetonitrile obxc
of -0.1. It is worth noting that the desilylation 308 nm) reveals as minor products acetophenone, its
competes efficiently with the photochemical dimer- enol, and 1,f-dibenzoylethane. The main photoproduct
ization even at fairly high concentrations of 48. The of 53 has not been isolated, but the CIDNP spectrum
result has been attributed to solvent interaction by observed during the photolysis is in agreement with
hydrogen bonding with the SI state of 48." the structure of the anthrone derivative 54, which is
CH3
formed by radical coupling. The photochemical rear-

m-m
H3C-hi-CH3

0 0 0 CH30H '0 0

48

As for 9-anthryl ketones in their electronic ground

state, their molecular geometry is such as to have the
anthracene and the carbonyl 7r-systems in mutually
perpendicular arrangement, so that electronic conju-
gation is negligible.197J98In their photoexcited state,
by contrast, 9-anthryl ketones can assume a geometry rangement of 53 also can be sensitized by biacetyl, but
in which the torsional angle between the anthracene CIDNP spectroscopy reveals that the formation of the
and the carbonyl group is drastically reduced, and rearrangement product 54 by direct excitation of a-(9-
intramolecular reactions involving the anthracene and anthry1oxy)acetophenone involves the excited singlet
Unbndecular Photochemistry of Anthracenes Chemicel Revlewcr, 1993, Vol. 93, No. 1 151
rather than the triplet state. An analogous mechanism
applies to the photolytic@-cleavageof other (a-aryloxy)-
ace top hen one^.^^ / H
-
-hv(b0.28)

hv(@-0.1) Ar '
The rearrangement of the anthracene derivative 55 0 Ai
by direct excitation to give the dearomatized product 61
56, formally, also proceeds by way of @-bondcleavage

H Ar Ar
(13 84 65

55 56 Y. Intramolecular Energy Transfer In SubstHutai

Anthracenes
and may be rationalized in terms of an intramolecular
triplet sensitization by the cyclopentenone moiety. In A. Photophyslcal Effects
line with the arguments presented in section V.A for Intramolecular energy-transfer reactions involving
interactions between photoexcited anthracenes and the anthracene r-system as one of the participating
aromatic ketones, intramolecular singletainglet energy chromophores have been investigated mainly by emis-
transfer from the anthracene chromophore to the sion spectroscopy,and the results have provided basic
cyclopentenone in 55 is energetically feasible because information about the dependenceof the rate of energy
of the favorable electron spectral overlap of the transfer on the distance between the donor and acceptor
anthracene absorption around 380 nm, and the ab- For a-(9-anthryl)-o-(l-naphthyl)alkanes
sorption due to the cyclopentenone n-r* transition. 66a-q the efficiencies of singlet energy transfer from
The subsequent intersystem-crossing step is assumed the naphthalene to the anthracene were found to be
to be an efficient process, as may be deduced from the identical for methano-, ethano-, and propano-separated
relatively low fluorescencequantum yield of 55 (0.05).206 ~ - ~ y s t e mIn ~ ~ compound 66d, where the donor
s .model
and acceptor r-chromophores are separated by about
Other examples of photochemical dearomatization of 20 A, the singletainglet energy-transfer efficiency was
9-alkyl-substitutedanthracenes characterized by a weak found to be about 0.84.58 By contrast, evidence for
@-bondhave been reported.207 triplet-triplet energy transfer in 66 was not obtained.59
Irradiation of 2-azidoanthracene (57) in dioxane-
methanol containing potassium methoxide yields, de-
pending on the workup conditions, either l-amino-2-
methoxyanthracene (59) or the azepine derivative 60
in excellent yields. The aziridine derivative58, deriving
from the primarily formed nitrene, is assumed to be
the reactive intermediate.208 The products deriving
from the carbene formed by photolytic decomposition
of di-9-anthryldiazomethanehave not been investigat-
ed.m

I
0=c:

b m
Reviews on various aspects of energy transfer have
been published previously, and intramolecular energy
59 60 transfer continues to be a topic of general interest.211-216
The following discussion will be limited to recent resulta
on the photophysical and photochemical consequences
The photochemical isomerization of l-(g-anthryl)- of singlet and triplet energy-transfer reactions involving
2-benzoylethylenes 61/62 leading to 5H-dibenzo[a,d]- anthracene derivatives.
cycloheptenes 65 proceeds smoothly, albeit with low
quantum efficiency, as a process competing with 1. Andhrecene-Tethered Dyes
geometrical cis-trans isomerization. The enlargement Intramolecular singlet energy transfer from an-
of the central ring of the anthracene *-system has been thracene to Rose Bengal has been established in an
rationalized by a 4r + 2u cycloaddition leading to 65 emission spectroscopic investigation of anthracene-
via intermediates 63/64.210 tethered derivatives.217The increase of the Rose Bengal
152 Chemical Revlewe, 1993, Vol. 93, No. 1 Becker

fluorescenceintensity was found to be less than expeded Table I. Fluorescence Quantum Yields of
from the degree of quenching observed for the emission o-(g-Anthryl)propiophenones70a-e in Cyclohexane and
Acetonitrile
from the locally excited anthracene. The excitation
spectra for the emission from anthracene-tethered Rose
Bengal derivatives differ from the corresponding ab- comd R R' CsHl2 CHsCN
sorption spectra, indicating the formation of intramo-
~~

70a H C& 0.41 0.066

lecular complexes. In those ground-state complexes, 7Ob CHIO H 0.20 0.075
the two chromophoresare suggestedto be in a proximate 700 H H 0.082 0.016
geometry conducive to fluorescence quenching. In- 7od CsHs H 0.04 0.0014
tramolecular complex formation has also been deduced 700 CH&O H 0.00056 O.oooO8
from the emission spectral properties of the 9-anthryl-
methyl ester of fluorescein, for which the efficiency of cage complexes, the aromatic a-system was found to
singlet energy transfer from the anthracene to the dye serve as an antenna sensitizer for the reduction of Co-
chromophore was calculated to be 0.38.218 (111) to C0(II).222.223
The fluorescence quenching ob-
In a recent study of a-chromophorically substituted served in the ruthenium complex of substituted bipy-
rhodamine dyes, energy transfer from the anthracene ridyl68 was found to be due to efficient intramolecular
to the rhodamine in trichromophores 67a was found to triplet energytransfer to the anthracene from the metal-
be associated with unexpected quenching of the to-ligand charge transfer state.224Likewise, in rhenium
rhodamine In the rhodamine model carbonyl complexes69, the metal-to-ligand excited state
lacking the anthracene antenna, the fluorescence was found to be efficiently deactivated by strongly
quantum yield is 0.96. The quantum yield decreases exothermic energy transfer to the lowest triplet state
to 0.22 in 67a when n = 1, and to 0.07 when n = 2. of the anthracene.225
Structural details about the ground-state geometry of
anthracene substituted rhodamine derivatives 67a are
not available, but it seems reasonable to assume that
increased flexibility of the linking chain facilitates an
intramolecular arrangement of the donor and acceptor
a-systems to the effect of fluorescence quenching,
conceivably by way of electron transfer. The decrease W i
(CO)3 Re'(b)-tac
in fluorescence quantum yield observed by tethering (18 69
the anthracene fluorophore to viologens such as in 67b
also has been attributed to intramolecular electron 3. Anthracene-Aryl Ketone Interactions
transfer.220
Excited-state interactions between anthracenes and
aromatic ketones have been studied mainly in bichro-
mophoric compounds such as 70 and 71, in which the
energy gap between the two interacting a-systems, and
the relative disposition of their excited-state energy
levels may be manipulated by appropriate substitu-
tion.6SJ10In both 70 and 71, the absorption spectral
properties of the aromatic carbonyl chromophores are
such as to preclude their selective excitation and to
make the transfer of energy from the photoexcited
anthracene to the ketone an endothermic process.
For w(9-anthry1)propiophenones 70 in nonpolar
m 2 PFe' solvents,the decrease of the fluorescence quantum yield
from 0.40 for 70a to <low3in 70e is associated with the
decrease in energy gap between the SIstates of the two
interacting a-systems. In polar solvents, the electron

Evidence for singlet energy transfer from the an-

thracene to the tetraphenylporphyrin a-system was
obtained by emission spectroscopy for terminally
substituted polyenes.221This finding is unique insofar 7- (see Table I)
as selective excitation of the anthracene a-system
around 256 nm is possible, and singlet energy transfer acceptor properties of the arylcarbonyl moiety are
apparently proceeds along the fully conjugated spacer. enhanced to the effect of facilitating fluorescence
quenching by electron transfer, as is evident from the
2. Energy Transfer Involving Metal Complexes drastically reduced fluorescence quantum yields in
Intramolecular energy-transfer reactions of metal acetonitrile (see Table I).65
complexescontaining covalently bound anthracene have Analogous substituent- and solvent-dependent flu-
been investigated in recent years in conjunction with orescenceproperties have been found for spiroanthronyl
the growing interest in electron transfer processes. In anthracenes 71.65 Moreover, in both 70 and 71, the
a study on the photoproduction of hydrogen from water charge-transfer mode of deactivation in polar solvents
by irradiation of anthracene-tethered hexaaza-cobalt is evident from the appearance of exciplex-like lumi-
Unlmolecular Photochemlsby of Anthracenes Chemlcal Reviews, 1993, Vol. 93, No. 1 158

thracene and fluorene *-systems in one of the two

diastereomers.
The photochemical isomerization of 9-anthrylmethyl
methyl maleate (76) in benzene solution to give 9-an-
thrylmethyl methyl fumarate (77) with a quantum yield
of 0.02 has been rationalized in terms of a triplet state
reaction.230 Since the energy of the triplet state of the
nescence. For example, the fluorescencequantum yield maleate chromophore is assumed to be about 72-77
for the locally excited anthracene in 71, R = methoxy, kcal/mol, triplet sensitization by intramolecular energy
decreases from 0.47 in cyclohexane to <0.001 in transfer from the photoexcited anthracene would have
chloroform, and the formation of an electronically to involve its T ~state.231*232
L
excited complex is indicated by a structureless emission
around 560nm.65J10The geometrical aspects of excited-
state complex formation from fairly rigid spiro com-
pounds 71 are of particular interest, as any sandwich
arrangement of donor and acceptor moiety is precluded
for structural reasons, and the excited-state geometry
78 TI
should closely resemble the geometry of the electronic
ground state.226~227
W I . Chemical Consequences of Intramolecular
B. Isomerlzatlons Involvlng Energy Transfer Electron Transfer
Chemical transformations by way of intramolecular During recent years, a multitude of reviews on
energy transfer generally involve the triplet state of photoinduced electron-transfer reactions have been
the anthracene chromophore. The photochemical di- p ~ b l i s h e d . ~Therefore,
~ ~ - ~ ~ ~ the discussion in this
*-methane rearrangement of 2,3-anthrabarrelene (72) section will be limited to some recent examples of
to give 2,3-anthrasemibullvalene(73) with a quantum intramolecular electron transfer induced photochemical
transformations of anthracene derivatives.
Most spectroscopicstudies of intramolecular electron
transfer involvingphotoexcited anthracenes have been
devoted to the formation of exciplexes with aromatic
amine^.^^^^^ Irreversible chemical transformations by
72 73
intramolecular electron transfer will lead to addition
yield of 0.25 represents an interesting example of an products derived from initially formed radical ions.
isomerizationwhich proceeds by intramolecular transfer Thus, irradiation of 9-(&anilinoethyl)anthracene (78;
of excitation energy from a higher triplet state of the n = 1) in benzene gives in 58% yield the dihydroan-
anthracene chromophore to the substituting divinyl- thracene derivative 79, whose formation resembles an
methane moiety.228It is worth noting that the skeletal electrophilic substitution of the anilino moiety. Only
rearrangement does not proceed by aryl-vinyl bridging, minor amounts of the amination product 80 are formed
that the isomerization cannot be sensitized by biacetyl in the photolysis of the (anilinoethy1)anthracene. Ir-
(ET = 55 kcal/mol), and that the TIstate of 2,3- radiation of 9-(3-anilinopropyl)anthracene(78; R = 2)
anthrabarrellene (-43 kcal/mol) is unreactive. Most was found to give intramolecular addition products 81-
likely, energy transfer occurs from the Tz state of the 83, although in low yield only (25%, 4%, and 496,
anthracene (ET = 74 kcal/mol) to the di-*-methane respectively).239
moiety (ET = 57 kcal/mol) undergoing vinyl-vinyl
bridging.
Photoexcitation of the anthracene *-system in dia-
stereomeric (9-anthrylethyl)spiro[cyclopropane-1,9'-
fluorenel-2-carboxylates 74 and 75 leads to a photo-
stationary state with a 74:75 ratio of 95:5. On the basis

78 79 80

of the degree of quenching by oxygen, the isomerization

of the cyclopropane stereochemistry has been suggested
to involve TPenergy transfer from the anthracene to
the fluorene and subsequent reversible cleavage of the
cyclopropyl bond.ns Photochemical isomerization ex- 81 82 83
periments with 74/75 prepared from optically active
cv(9-anthryl)ethanolprovided evidence for asymmetric The chemical consequences of intramolecular pho-
induction by intramolecular TZenergy transfer due to toinduced electron transfer involvingthe excited singlet
geometrically enhanced interaction between the an- state of the anthracene *-system as donor moiety, and
154 Chemical Reviews, 1993, Vol. 93,No. 1

sulfonium groups as electron acceptors are rearrange- to be a prerequisite for the cleavage to occur, as benzyl
ment and solvolysis reactions. For example, photoex- 9,10-dimethoxyanthracene-2-sulfonate was found to be
citation of the anthracene chromophore in (p-cyanoben- ph~tostable.~~.~~~
zyl)methyl(9-anthryl)sulfonium hexafluorophosphate
(84) in acetonitrile (A > 400 nm) gives hexafluorophos-
phoric acid (100% yield) with a quantum yield of 0.77,
and all five regioisomeric (p-cyanobenzyl)-substituted
9-(methy1thio)anthracenes85 (56% yield) with a quan-
tum yield of 0.43. The relative preponderance of the

-
hv m-
/ /
C H 2 O C N

/
V I I . Excnec-State Reactions ot
Anthwi-Substituted Alkenes, AzmetMnes, and
Azines
Photochemical transformations of anthryl-substi-
tuted alkenes, particularly their geometrical isomer-
CN ization, have been investigated extensively during the
84 85 past 10 years, since it was found that various anthryl-
substituted trans-alkenes resist photochemical con-
9,lO isomer (68%)over the 1,9 (E%), 2,9 (lo%),3,9 version to the cis isomer.100J02~248,247
The mechanistic
(2%),and 4,9 isomers ( 5 % ) has been attributed to a aspects of photochemical one-way isomerization of
9,lO-bridged sulfonium ion intermediate. Solvolytic aromatic olefins are being reviewed elsewhere in the
formation of 9-(methy1thio)anthraceneand the N-acetyl current issue of Chemical Reviews. As for the photo-
derivative of p-cyanobenzylamine, proceeding with a chemical s-cis/s-trans isomerization (rotamerization)
quantum yield of 0.34, competeswith the photochemical of anthryl-substituted alkenes such as 93a/93b,this
rearrangement. Likewise, irradiation of the 9-phenyl- topic has recently been treated comprehensively and
anthracene derived sulfonium salt 86 in acetonitrile will not be considered here.68*248
was found to give rearrangement products 87 (0= 0.15)
and the corresponding solvolysis products (0 =
0.17).240*241 &+yJJq-
/ / /

hv /
830 em

A. Geometrlcal Isomerltatlon and Cycloaddltlon

Reactlons
Upon irradiation in dichloromethane solution, (9-
anthry1)alkenes 94-97, in which the alkene is conju-
gs e?
gatively substituted by either carbonyl or nitro groups,
There can be little doubt that the benzylic character undergo reversible geometrical isomerization in dichlo-
of the substituent enhances the efficiency of the bond romethane solution (see Table 11). In the case of the
nitrovinyl substituted anthracenes 96/97,the quantum
cleavage/radical coupling reaction observed for sulfo-
nium salts 84 and 86. The photolytic cleavage of benzyl
bonds by photoinduced electron transfer has been
studied in numerous bimolecular reactions involving
dependent. In benzene solution, E Z isomerization
of 96a and 96b proceeds with quantum yields of 0.20
-
yields of geometricalisomerization are markedly solvent

photoexcited 9,lO-dicyanoanthracene as electron ac- and 0.14, r e ~ p e c t i v e l y . ~ ~ ~ * ~ ~

ceptor.H2 Indeed, the quantum yields of acid formation
found in the photolysis of anthrylsulfonium salts 88-
90lacking the benzyl moiety are quite low (-0.1-2 %I ).243
Moreover, the quantum yields are dependent on the
excitation wavelength.
&+A/ /

W b
/

a:R.CH&O
0 0

W0-b
0

q b: R I C&CO

Gs;:
88 8s
SbFs

90
4
The formation of 9,10-dimethoxyanthracene-2-sul-
fonic acid (0 = 0.101, p,p-dinitrobibenzyl, and 9,lO-
dimethoxy-2-(p-nitrobenzyl)anthracene(92)by pho-
toexcitation of the anthracene chromophore in p- Geometrical isomerization and competing intramo-
ni trobenzyl9,lO-dimethoxyanthracene-2-sulfonate(91) lecular cycloaddition reactions characterize the pho-
in acetonitrilesolution is typical of radical ion chemistry. tochemistry of (9-anthry1)alkenes which contain an
The presence of an electron-withdrawing substituent additional anthracene chromophore (cf. section V1II.B).
in the para position of the benzyl moiety appears Thus, irradiation of trans-1,3-di(9-anthryl)propene(98)
Unimolecular PhotochemisQ of Anthracenes Chemical Revlews, 1993, Vol. 93,No. 1 155

Table 11. Quantum Yields of E / Z Isomerization of the anthracene preclude planar ground-state confor-
(9-Anthry1)alkenes94-97 in Dichloromethane mations, so that electronic conjugation of the styryl
a and anthracene x-systems is impaired even for the trans
compd R E-4 Z-E ref isomer 10Sa.lo3 In cyclohexane solution, cis-Bstyryl-
94496a CH&O 0.39 0.32 102
94b195b CSHSCO 0.28 0.1 102
96aI97a H 0.008 0.005 249
96b197b Me 0.055 0.004 250

in benzene smoothly gives the cycloaddition product

100, albeit with low quantum yield (<0.001). Attempts
to detect by absorption spectroscopy the intermediate
cis isomer 99 during the course of the reaction have not
been successful, because the quantum yield of in-
tramolecular cycloaddition of 99 is far higher (0.25).'02 anthracene (107a) is photochemically converted into
Similar features characterize the photochemical isomer-
ization of trans-1,3-di(9-anthryl)propenone(101). -
the trans isomer lOSa with a quantum yield of 0.22, but
the reaction is irreversible, i.e. trans cis isomerization
is not observed in cyclohexane, although lOSa reacts
slowly (@ = 0.0014) to give some unidentified prod-
U C ~ . Time-resolved
~ ~ ~ * ~ ~ fluorescence
~
ments reveal the photochemical cis - decay measure-
trans isomer-
ization of 9-styrylanthracenes to proceed adiabatically.
Significantly, polar solvents and polar substitutenta in
the para position of the styryl group (see Table 111)
have been found to facilitate the photochemical trans
-cis isomerization of 9-styrylanthracenes, conceivably
by way of intramolecular electron-transfer processes.
For the NJV-dimethylamino derivative 10Sb, trans -
-
cis isomerization is remarkably efficient in cyclohexane.
The trans cis isomerization of the nitro derivative
lOSh is worth noting, as it proceeds with lower quantum
efficiency in acetonitrile than in cyclohexane. Formyl
-
101 102 103
substitution of the 10-positionof the anthracene moiety
trans,trans-Dianthrylpentadienone104 isomerizes virtually quenches trans cis isomerization in lOSi,
photochemically in oxygen-saturated solution to give possibly by altering the character of the lowest excited
a mixture of cis,trans isomer 105 and the cis,cis isomer
106. However, irradiation of 104 under nitrogen
smoothly leads via the cis,trans isomer 105 to the
cyclomer 55. Ita formation from 106 involves the Diels-
State.
Even in the absence of polar substituents, trans
cis isomerization can' be enhanced in polar solvents.
-
The trans isomeric anthryl naphthyl ethylene 110
Alder addition of the trans-(g-anthryl)alkene double
bond to the central ring of the other anthracene moiety.
The quenching by oxygen suggests that the 4x + 2?r
in cyclohexane, but the trans -
cannot be converted into ita cis isomer 109by irradiation
cis isomerization
proceeds smoothly in acetonitrile, albeit with low
cycloaddition proceeds as a triplet-state reaction, while quantum efficiency.
the geometrical isomerization of 105/ 106 involves the
excited singlet state.lo2(For the photolytic rearrange-
ment of 55, see section IV.)

Substitution of the carbon-carbon double bond in

rrms,rrans
1M
ais.ms
105
\
/
\
/
&,,h
106
\
/
9-styrylanthracene by either methoxy or nitro groups
also was found to facilitate photochemical E
isomerization. For example, the photochemical con-
Z -
version of the 11 la,b into their corresponding2 isomers
Iv
4~ + 2n qclomer
112a,bproceeds in cyclohexanesolution with quantum
yields of 0.23 and 0.14, respectively. The corresponding
55 quantum yields for the reverse reaction are 0.23 and
0.045, respectively.
Considerable experimental and theoretical efforts The photochemistry of the parent trans-1,2-di(9-
have been devoted to the photochemistry of styryl- anthry1)ethylene (114a) resembles that 9-styrylan-
a n t h r a c e n e ~ . ~ It
l -has
~ ~ been
~ established for both cis- thracene lOSa insofar as geometrical isomerization of
and tram-9-styrylanthracene (107a/ 10Sa) that steric the ethylene double bond is not observed. Surprisingly,
repulsions involving the vinyl group and H-1/H-8 of the cis isomer 113a also is characterized by extremely
156 Chemical Revlews, 1993, Vd. 93, No. 1

Table 111. Quantum Yields of Geometrical Table IV. Quantum Yields of Geometrical
Isomerization of Substituted 9-Styrylanthracenes Isomerization and Cycloaddition for
107/108 in Cyclohexane and in A c e t ~ n i t r i W ~ l , " ~ l,!&Di(S-anthryl)ethylenes113/114 (in CeHlr)
113/114 R* R* 114-113 113-114 113+cycl addition
cis-trans trans-cis a H H <<0.0001 0.0007 0.0007 4r+2r
R' R2 (C&dCH&N) (CsHdCHsCN) b H CHO 0.22 0.015 <0.001 4r+2r
c H MeOCO 0.20 0.015 <0.001 4r+2r
107a/lOSa H H 0.22/0.41 <0.01/0.003 d H Me0 0.088 0.053 0.0012 4r+4r
107b/108b H NMez 0.18/0.40 0.24/0.22 e Me0 Me0 0.26 0.049 0.0025 4r+4r
107c/10& H OMe 0.17/0.25 0.0210.33 f Me Me0 ? <0.01 0.20 4r+4r
107d/108d H Me 0.19/0.36 <0.01/0.18
107e/lOSe H CN 0.47/0.46 <0.01/0.41 anthracene 7r'-systems,undergoes intramolecular 4 r +
lOlf/lOSf H CHO 0.7010.35 0.02/0.38
107g/lOSg H C&&O 0.45/0.32 0.20/0.26 47r cycloaddition with a quantum yield of 0.20.'@
107h/108h H NO2 0.51/0.05 0.13/0.02 Irradiation of di-9-anthrylcyclopropenone (117) in
107i/lOSi CHO H 0.41/0.34 010 cyclohexane, by contrast, does not result in dianthryl-
107j/tOSj CHO C&&O ? o/o ethylene photochemistry,but decarbonylationsmoothly
leads to di(9-anthrybacetylene (118)with a quantum
yield of 0.14.108+2so

AA
n

A-CEC-A
A

Unexpectedly, the photochemical isomerization of

the 9-anthryl-substituted enol 119 in dichloromethane
inefficient photochemistry. The conversion of 113a into gives the 9,lO-dihydroanthracene derivative 121 (0=
0.18). It has been suggested that the photochemical
A\C/ R' hv A\/' step leads to the intermediate ketone 120 which
II c- II isomerizes by way of a ground-state 1,7-hydrogen
hv Rz'c\A
shift."
11a-f A-9-mlWl 114a-f
(seeTable IW

the trans isomer 114a proceeds in cyclohexane with a

quantum yield of only 0.0007, (0.015 in chloroform),
and equally inefficient is the isomerization of 113a by
47r + 27r cycloaddition to give 115 (0 = 0.0007),and by
47r + 47r cycloaddition to give 116 (0< 0.0007).25s~269 119 12Q 12l

The photophysical and photochemical properties of

9-anthryl-substituted azomethines 122/123 (R= H,Br,
NO2) have recently been investigated. For R = NOz,
the involvement of the excited triplet state in the
geometrical isomerization has been suggested.261The
excited-state properties of (E)- and (2)-N-methoxy-
1-(2-anthry1)ethanimine(124/125)have recently been
studied in detail with respect to both geometrical and
rotational isomerism.262
115 116 7
Substitution of the ethylene bond profoundly affects
the excited-state properties of 1,2-dianthrylethylenes
Q
H
. C//N
113/114,as it changes their ground-state molecular
geometry to the effect of increasing the dihedral angle
between the ethylene and anthracene 7r-systems.10g
Significantly,trans to cis isomerization is observed, the 122 123
cis isomer is favored at the photostationary state, and
quantum yields may be as high as 0.26 (see Table IV).
Moreover, as the dihedral angle between the ethylene fH3 hv
and anthracene 7r-system increases by substitution,
photochemical isomerization of cis-dianthrylethylenes
by Diela-Alder reaction becomes negligible, and in- 124 125
tramolecular 4n + 47r cycloaddition is predominant.
Dianthrylethylene 113f,for which electronic absorption The photochemical geometrical isomerization of
and emission spectra, as well as X-ray diffraction data various 9-anthryl-substituted azines has been of interest
indicate enhanced intramolecularinteraction of the two in conjunction with their photochromic properties.-286
Unknolecular photochemistry of Anthracene8 Chemicel Revlews, 1003, Vol. 03, No. 1 157

The distinctly different emission spectral properties of

the photochemically interconvertible three isomeric
9-anthraldehyde azines 126-128 are attributed to dif-
ferences in their molecular geometry.2ss

V I I I . Isomer&atlon of Non-ConJugatlve& Llnked

Bkhromophork Anthracenes
Photoexcited bichromophoric anthracenes charac-
B. Dehydrocycllzatlons terized by a weak link in the connecting chain of atoms
may deactivate by way of fragmentation. For example,
Intramolecular photochemical dehydrocyclizations irradiation of (9-anthry1)methyl sulfides, disulfides,
of anthracene-related compounds are well known for selenides, and diselenides (138-141;A= 9-anthryl)leads
bianthrone and similar stilbene-like anthrone deriva- to the 4 r + 4u photoisomer of 1,2-di(9-anthryl)ethane
t i v e ~ . % ~In
- ~recent
' years, several examples of styryl- and to lepidopterene (see below), i.e. products derived
substituted anthracenes undergoing photochemical by dimerization of (9-anthry1)methyl radical 143a/
dehydrocyclizationhave been reported. Irradiation of 143b.277*278 Photoexcitation of (9-anthry1)methyl (9-
styryl-substituted anthracene 129 in xylene for 60 h anthryllacetate (142) also gives (9-anthry1)methyl
gave 130 in 15% yield.272*273 The photochemical con- radicals by way of decarboxylation, and the high
version of the tetradecyloxy-substituted1,2-di(l-an- quantum yield of disappearance of 142 (a = 0.38)
thryllethylene 131 into the dibenzopicene 132 (15% probably is attributable to the formation of the 1,2-
yield) is of interest because the conceivable isomer- di(9-anthryllethanephotoproduct and lepidopterene,
ization of 131 by 47 + 4x cycloaddition was not +
rather than an intramolecular 4u 4u cycloaddition
observed.274 product of (9-anthryllmethyl (g-anthryl)acetate, as has
been s u g g e ~ t e d . ~ ~ ~ * ~ ~
A A A
I I I
A CH2 A CHz CHI
I I I I I
CHz S CHz se c=o
I I I I I
S
I
FHz
S
I
CH2
ryz se
I
CHZ
0
I
CH2
I I
A A A A' A
138 139 140 141 142

Unimolecular photochemistry of compounds con-

taining two anthracene moieties frequently involves
The conversion l-(Y-anthryl)-4-phenyl-l,3-butadiene isomerization by intramolecular 4 s + 4u cycloaddition,
(133)leading to the dibenzopyrene 134 (7% yield) by as was first observed by the conversion of 9-anthroic
anhydride (144) into 145.21f32 Structurally similar
compoundssuch as the carbonate 146,amide 147,and
the azo compound 148 (A = 9-anthryl) were found to

way of two consecutivecyclization and dehydrogenation

144 145
steps requiring 84 h of irradiation obviously is very
i n e f f i ~ i e n t .By
~ ~contrast, irradiation of 135 in toluene
0 0
in the presence of iodine in an argon atmosphere II II
A-0-C-0-A A-0-C-NH-A A-NZN-A
afforded 136 in 93% yield by a remarkable 4-fold
cyclodehydrogenation. The reaction is of considerable 146 147 148
synthetic interest because dehydrogenation of 136 with
2,3-dichloro-5,6-dicyanobenzoquinone (DDQ)proceeds undergo intramolecular 4u + 4u cycloaddition in the
smoothly to give circumanthracene (137).276 same fashion.281In principle, the photochemical isomer-
158 Chemical Reviews, 1993, Vol. 93. No. 1

ization of bichromophoric anthracenes thus resembles been detected in rigid solution, and it has been
the bimolecular reaction of anthracene. However, established, that the cycloaddition reaction involves
subsequent systematic studies on bichromophoric an- deactivation of the excimer state.m In a process
thracenes have revealed that other modes of cycload- competing with the intramolecular 4 r + 4u cycload-
dition than 4u + 47r head-to-head dimerization are dition, 151 undergoes geometrical isomerization to give
possible. By and large, the unimolecular photochem- anti-[2.2](1,4)anthracenophane (153) which is char-
istry of non-conjugatively linked bichromophoric an- acterized by structured fluorescence (@ = 0.27).%
thracenes is found to be intimately related to their Probably due to steric constraints, [2.51(9,lO)anthra-
ground-state molecular geometry and may also be cenophane (154)does not isomerize photochemically
governed by substituents which affect the intrinsic by cycloaddition.292
quantum yield of intersystem crossing from the excited Several [3.31(1,4)naphthaleno(9,lO)anthracenophanes
singlet to the triplet state. and diaza[3.3lparacyclo(9,10)anthracenophanes such
as 155 and 156 have been found to undergo thermally
A. Anthracenophanes and Anthraceno Crown reversible photoisomerization by 4u + 4u cycloaddition
Ethers with quantum yields of about 10-30%.295-m As for
dithia[3,3lparacyclo(9,l0)anthracenophanes,their pho-
The spectroscopic and photochemical properties of tochemistry is characterized by sulfur extrusion, as
anthracenophanes, crown ethers, and cryptands have exemplified by the conversion of 157 into 15tIaw This
been reviewed previously, so that only some principal type of reaction has been of value in cyclophane
features of their photochemistry are outlined be- synthesis. However, attempts to extrude sulfur by
low.39,283
irradiation of dithia13,31(2,7)anthracenophane have not
The thermally reversible photochemical isomeriza- been successful.B8
tion of 12.21(9,lO)anthracenophane (149) has been
investigated most thoroughly, and the structures of both
149 and its photoisomer formed by intramolecular 417
+ 47r cycloaddition have been established by X-ray
diffraction.282-290 The anthraceneskeletons in 149were
found to be bent about the 9,lO-axis by 19 (161), and
the distance between the bond-forming carbon atoms A d
(9,9:10,10) is only 2.77 A.26g Photochemical isomer- 155 156
ization of 149 proceeds even in rigid matrix at 4 K. In
solution at room temperature (and at 77 K), anthra-
cenophane 149 is nonfluorescent, there is no excimer
state observable, and the quantum yield of photo-
chemical isomerization is 0.36. Evidence for biradical
157 158

The photochemical isomerization of polyether-linked

bichromophoric anthracenes such as 159 (X = 0)has
been studied e x t e n ~ i v e l y Quantum
. ~ ~ ~ ~ yield
~ ~ mea-
surements have revealed that a,w-dianthryl polyethers
149 1
- a:n-1
kn-2 may isomerize much more efficiently than the corre-
sponding a,w-dianthrylalkanes. For example, the a,w-
di-9-anthryl-substitutedpolyether 159 (X = 0)isomer-
izes upon irradiation in benzene by 4u 41r cyclo- +
addition with a quantum yield of 0.32 to give a thermally
labile cyclomer (t1p ca. 3 minhm By contrast, pho-
toexcited l,lO-di(9-anthryl)decane(159;X = CH2) in
152
benzene disappears with a quantum yield of ClW,
151
conceivably in a bimolecular reaction (see section
HE-CHI VIILB).
A-X A X -XAX-A
159 A I S-anthwl

Due to changes in molecular geometry, the course of

15.3 154 the photochemical isomerization of anthraceno crown
ethers may be affected by the presence of complexed
intermediates in the photochemical reaction and the metal ions. Thus, irradiation of the sodium ion
thermal cycloreversion has not been obtained.262*288 complexed bis(anthracen0) crown ether 160affords the
Other anthracenophanes undergoing photochemical 9,9: 10,lO-symmetrical isomer formed by 4u + 4u
isomerization by 41r + 4u cycloaddition are L2.31- cycloaddition,while irradiation in the absence of sodium
(9,lO)anthracenophane (150a), [2.41(9,10)anthra- ions leads to the dissymmetrical isomer formed by 1,9:
cenophane (Gob),syn-12.21(1,4)anthracenophane(1511, 4,lW 4 r + 417 cy~loaddition.~For more rigidly linked
and [2.2](1,4)(9,lO)anthracenophane (152).2a*2w>B11B2 anthraceno crown ethers of limited intramolecular
For anthracenophane 151, excimer fluorescence has mobility, such as 161,metal complexation has been
Unholecular photochemistry of Anthracenes Chemlcel Reviews, 1983, Vd. 83, No. 1 158

Table V. Quantum Yields of Fluorescence (*p) and

Isomerization (h) for Di-(9-anthry1)methane
Derivatives 162,164,and 166
compd @F solvent cycloaddition
162a 0.06 0.15 benzene 4r + 4r
162b 0.02 0.29 benzene 4 r + 4r
162c 0.02 0.05 benzene 4 r + 4r
164 0.18 0.45 toluene 4r + 2r
166 <0.0001 0.0003 benzene 4r + 2 r ogous photochemical intramolecular Diels-Alder re-
action of di(9-anthryl) ketone (166)leading to 167.307
found to be without effect on the efficiency of photo-
chemical isomerization by intramolecular 4s + 4r m
cycloaddition.301

W
166 167

The ground-state structures of 162a,b,164,and 166

have been analyzed by X-ray diffraction, and the
topological differences between dianthrylmethanol and
dianthryl ketone were found to be insufficiently small
to account for the difference in the observed mode of
hv l,Q'-4,10'-
photochemical isomerization.m*m*mSince the isomer-
[ 4 ~ + 4cydomec
~] ization of dianthryl ketone also was found to proeeed
0 I4 X lo4 in a biacetyl-sensitized reaction (@R = 0.005), the
observed 4 r + 2a cycloaddition by direct excitation of
166 probably is due to an excited triplet state reaction.
As for the 4 r + 2 s cycloaddition mode of 164, the
reaction apparently does not involve the excited triplet
state,since its quantum efficiency is virtually unaffected
by the presence of molecular oxygen. It is worth noting
that the distance between the Diels-Alder termini C-9
and C1' in 164 is as short as 2.86 A and that the 4r +
2 s cycloaddition of 164 also can be brought about in
a thermal reaction.309
The excited state properties of 1,2-di(9-anthryl)-
161
ethane (168a)have been most frequently and thor-
B. Dianthrylalkanes and Their Derivatives oughly investigated during the past 25 years.B2$1*s1s
Deactivation of the first excited singlet state by
Pertinent excited-state properties of di(9-anthry1)- fluorescence and by intramolecular 4s + 4~ cycload-
methane derivatives 162 are summarized in Table V. dition to give 169a proceeds with quantum yields of

*& L x
Both di(9-anthrybmethane (162a)and di(9-anthry1)- 0.20 and 0.26, r e s p e c t i ~ e l y . ~Oxygen
~ * ~ ~ quenching
~*~~~
methanol (162b),and its 10-methoxy derivative 162c,
isomerize photochemically by 4s + 4s cycloaddition to
give the corresponding cyclopropane derivatives 163a-
By contrast, the photochemical isomerization of

0 0

experiments indicate that the triplet state may con-

x \
tribute slightly to the isomerization in thoroughly
degassed solution.310Significantly,biacetyl-sensitized
A 0 isomerization of dianthrylethane 168a has been found
+ +
to involve 47r 2 r (rather than 4s 4r)cycloaddition
16- %R'.e-H
b: R'
C: R'
-
I
OH; R2- H
OH; R
'. OCHS
1
-
to give 170a with a quantum yield of 0.1.31sHowever,

the methyl ester of 9-anthrilic acid (164)proceeds by

4s + 27r cycloaddition to give 165.= The observed
quantum efficiency of 0.45 is exceptionally high for a
photochemical Diels-Alder reaction involving two an-
thracene 7r-systems, and may be compared to the
quantum yield of 0.0003 which characterizes the anal- 1Wl
hv
__c

biaCatyl
8, 1ToI
-
160 Chemical Reviews, 1993, Vol. 93,No. 1

Table VI. Substituent Effects on the Quantum Yields Table VII. Quantum Yield8 of Fluoreacenca (h)in
of Fluorescence (OF) and Isomerization of Cyclohexane and Quantum Yields of Isomerization by
Dianthrylethanes 168 by Cycloaddition (OB)in 4r + 4% Cycloaddition (h) in Benzene for
1,3-Di(9-anthryl)propene&rivativesm
168 R' R2 @ F h tip of 169" propano-likedanthracene @F @st
a H H 0.20 0.26 385 years 1,3-di(9-anthryl)propane 0.47O 0.14O
b H CH3 0.15 0.26 38 years 1,3-di(9-anthryl)-l-propanol 0.27 0.14
c H CHsO 0.14 0.24 39 years 1,3-di(9-anthryl)-2-propanol 0.48 0.046
d H CH3COO 0.40 0.14 130 years 1,3-di(g-anthryl)-2-methyl-2-propanol 0.24 0.021
e H cas 0.61 0.034 187 days 1,3-di(9-anthryl)-2-propanone 0.009 0.26
f CH3 CH3 0.16 0.14 33 min 1,3-di(g-anthryl)-2-butanone 0.007 0.22
g CHsO CH30 0.30 0.11 142 min l,3-di(9-anthryl)-l-butanone <0.001 0.40
h CHsCOO CH3O 0.45 0.068 260 min 1,3-di(9-anthryl)-l-propanone <0.001 0.66
i CH3COO CH3COO 0.74 0.015 234 min 1,3-di(9-anthryl)-2-methyl-
1-propanone <0.001 0.72
a t1lz is the half-life in solution at 25 O C . a In methylcyclohexane;from ref 311.

triplet-sensitized isomerizations of non-conjugatively For photoexcited 1,2-di(9-anthryl)ethanone(173),the

linked anthracenes will proceed by 47r + 47r cycload- mode of isomerization by intramolecular cycloaddition
dition, if the molecular geometry of the electronic has been found to be concentration dependent. Irra-
ground state facilitates parallel alignment of overlap- diation of 173 at low concentration (O.ooOo3 M)affords
ping anthracene moieties, as is typical for propano- mainly the twoDiels-Alder products 174and 176,while
linked aromatic *-systems (see below). +
the 4 1 47r cyclomer 176 is formed nearly exclusively
The effects of 10,lO' substitution on the quantum by irradiation at higher concentration (0.0076 M).
yields of fluorescence and 47r + 47r cycloaddition of Dianthrylethanone is virtually nonfluorescent, and the
dianthrylethanes and on the stability of the photo- quantum yield of intersystem crossing has been esti-
isomers are summarized in Table VI.314 For the mated to be about 0.6. Therefore, the 4 r + 27
isomerization of dianthrylethanes 168,a quantum yield cycloadditionsconceivablyinvolve the triplet state. The
of 0.26 appears to be the upper limit. Fluorescence 4a + 4u cyclomer 176 has been suggested to derive
quantum yields increase noticeably as quantum yields from the excited singlet state whose population at higher
for isomerization decrease due to steric impairment by concentration could be attributable to triplet-triplet
substitution. The fluorescence quantum yield of the annihilati~n.~~*~~~
10,lO'-diphenyl derivative of dianthrylethaneis as high
as 0.79, and photochemical isomerization has not been
detected.314
The short half-life at room temperature of the
dimethyl substituted 47r + 47r cyclomer 169f is worth
noting in conjunction with the fact that irradiation of
168f at 70 "C affords the thermally more stable
photoisomer 170f,which derives from dianthrylethane c=o \
168f by a competing photochemical 47r 27r cycload- +
dition reaction of low quantum efficiency.317 It is
173

176

The photochemical isomerization of various other

ethano-linked anthracenes has been investigatad. Both
1691 1881 17U 1,2-di(9-anthryl)ethanol(177)and 9,9'-anthroin (178)
isomerize by 47r + 47r cycloadditionwith quantum yields
conceivable that the photochemical isomerization of of 0.34 and 0.21, r e s p e c t i ~ e l y . ~ ~Di(9-anthry1)-
~~l*~~~
168f by 47r + 27r cycloaddition involves the excited ethanedione (179;9,9'-anthril) upon irradiation gives,
triplet state. The photochemical isomerization of 10- among various decomposition products, an isomer
benzoyl-l,2-di(9-anthryl)ethane(171;@F = 0.002)lead- derived by intramolecular Diels-Alder reaction.320
ing to the 47r + 277 cyclomer 172 also proceeds with low However, the 1,Zcyclobutanedione 181 is accessible
quantum yield (0.0051,and evidence for a triplet-state from the anthroin photoisomer 180.
reaction in that case has been obtained by biacetyl
sensitization. ?H ?H B R B
A-C-C-A
A-CH2-v-A A-Y-C-h
H H

17? 178 179

A I O-anthryl
I hv $v

171 h 172
im
0
181
Untlar Photochemistry of Anthracenes Ctmmical Rovbws, 1883, Vol. 83, No. 1 161

meso-Hydro-9,9-anthroin(182)isomerizes photo-
chemically (@ = 0.15) by 4r + 4r cycloaddition, but
gives two stereoisomeric (cis and trans) 1,2-cyclobu-
tanediols 184/185. The formation of the trans isomer
185 indicates photoexcited meso-hydro-9,9-anthroin
undergoes stereoisomerizationto give racemic d,Z-hydro-
9,9-anthroin (183)by reversible scission of the central
single bond.

1 1 187

182 183
Photochemical isomerization by intramolecular 4 r
Ihv 1 hv
+ 4% cycloaddition has been established for 1,4-di(9-
anthry1)butane (@R = 0.061), but not for any of the
higher a,w-di(9-anthryl)alkane homologues. It ie ob-
vious from the quantum yields of reaction (@& of
fluorescence from the locally excited state (&M), and
of excimer fluorescence (hexC) listed in Table VI11 that
184 18.5 deactivation of the first excited singlet state by fluo-
rescence becomes dominant when intramolecular cy-
The photochemical isomerization of propano-linked cloaddition becomes less favorable?ll In line with
bisanthracenes 186-195 (A = 9-anthryl) has been found earlier observations on a series of a,w-dipyrenylalkanes,
to occur exclusively by 4r + 4r cycloaddition, and quantum yields of excimer luminescence vary with the
typical quantum yields of reaction and fluorescence length of the alkane chain.3u For 1,2-di(g-anthryl)-
are summarized in Table VII?22 Both l,&di(g-anthryl)- ethane and 1,3-di(9-anthryl)propane,the question of
excimer formation continues to be of interest, although
A A A A
I I I I excimer emission has been detectable only under special
CHI
I
CHZ
I
CHZ
I
CH2
I environmental conditions.32b331
CHI
I
CH2
I
H-C-OH
I
HG-C-OH
I
In a recent emission spectroscopic investigation of
FH? H-C-OH
I
FHZ FHz a,w-di(9-anthryl)alkanesof varying chain length (C3,
A A A A Cg, C7, CIO,C12, C14, and CIS),picosecond time-resolved
188 187 160 189 measurementshave revealed intramolecular excitation
hopping for photoexcited 1,7-di(9-anthryl)hepteand
HO CH. Ho 4 its higher homologues.332
It should be pointed out that the quantum yields of
disappearance of a,w-di(g-anthryl)alkanesare not to
1901 1- be considered quantum yields of isomerization, because
intermolecularcycloaddition may become an important
1-butanols 190a (lR,3S/lS,3R)and 190b (lR,3R/lS,3S) competing reaction if intramolecular cycloaddition
isomerize with identical quantum yields (0.23), but proceeds with low quantum yield. Thus, irradiation of
stereochemical differences may be reflected in the di-9-anthrylsuccinate (198)was found to give a polymer
different quantum yields of fluorescence (0.15 and 0.07, by intermolecular head-to-tail 417 + 4r cycl~addition.~~
respectively). Photochemical isomerization of racemic +
Polymer formation by intermolecular 4r 47r cycload-
1,3-di(9-anthryl)propan-l-o1(187) in a chiral matrix of ditions of various linked bis-anthracenes has been
poly(methy1tglutamate) was found to proceed enan- studied in some For a series of bisan-
tioselectively. At 90 % conversion, an enantiomeric thracenes derived from 1-anthracene-and 2-anthracene-
excess of more than 30 % was observed. In a separate carboxylic acid, such as 199,irradiation was found to
experiment, it was established that the 1 isomer of 187 give both intramolecular head-to-head and head-to-
+
undergoes intramolecular 4r 4r cycloaddition about tail 4r + 41 cycloaddition products.397 The photo-
20% faster than the d isomer.323 chemical isomerization of di-9-anthryl glutarate (200)
The involvement of the excited triplet state in the has been found to involve a head-to-tail 47r + 4r
isomerization by 4r + 47r cycloaddition has been cycloaddition, although another major photoproduct
established by oxygen quenching and sensitization of unknown structure is formed as
experiments for nonfluorescent propano-linked an-
thracenes 193-195 which are characterized by the
presence of a 9-anthroyl group. The highly efficient
isomerization of 1,3-di(9-anthryl)-l-propanone (193;@R
= 0.65) and its 2-methyl derivative 195 (@R = 0.72)
probably reflects an excimer geometry of parallel
aligned overlapping anthracene r-systems. Spatially
more crowded diastereomeric 1,3-di(9-anthryl)-2-meth-
yl-1-butanones 196 (2R,3S/2S,3R) and 197 (2R,3Rl
2S,3S) undergo intramolecular 4r + 4r cycloaddition The problem of intermolecular reactions competing
with quantum yields of 0.19 and 0.17, respectively. with intramolecular photochemistry of bichromophoric
162 Chemical Revlews. 1993, Vol. 93, No. 1

Table VIII. Quantum Yields of Reaction (*a), Monomer

Fluorescence (&), and Excimer Fluorescence (@F-~)
for a.o-Di(9-anthryl)alknes in Methylcyclohexane.
alkane a9.t @Flu h . e

butane 0.061 0.34 0.02

pentane 0.0011 0.31 0.16
hexane 0.0011 0.38 0.06
heptane 0.0012 0.37 0.04
octane 0.0011 0.33 0.14 stitution of the 9,9' positions by dimethylsilyl groups
nonane O.OOO6 0.30 0.21 makes photochemical isomerization of di(9-anthryl)
decane O.OOO4 0.39 0.08 compounds by symmetrical 4 r + 41 cycloadditions
a From ref 311. highly unfavorable for steric reasons. Thus, di(9-
anthry1)dimethylsilane (204)isomerizes by 4 r + 2 r
compounds can be circumvented by irradiation of very cycloaddition, involving as Diels-Alder termini the
dilute solutions, as was noted for photochemical 9,lO and 1',2'positions of the two anthracene r-system,
isomerization of 1-(9-anthry1)-3-(l-naphthyl)propane to give 208.346*34s Di(9-anthry1)dimethylgermane has
(201).339-343Irradiation at low concentration (2 X been reported to react in the same manner.3M The
M) smoothly gives the intramolecular 4 r + 4a cyclomer, photochemical isomerization of 1,3-di(9-anthyl)-l,1,3,3-
while irradiation at concentrations higher than M tetramethyldisiloxane (205),bis[(9-anthryl)dimethyl-
results in intermolecular 4a + 4 r cycloaddition in- silyl]methane (206),and 1,2-bis[(9-anthrylldimethyl-
volving two anthracene moieties. This finding suggests silyl)]ethane (207)does proceed by 4 r + 4 r cyclo-
that 4a + 4 r cycloadditions of anthracene to naph- addition, but the reaction involves the 9,lO-carbon
thalene proceed with low quantum yield. It is worth atoms of one anthracene, and the 1,a-carbonatoms of
noting that neither 202 nor 203 isomerize upon irra- the other, giving the corresponding cyclomers of struc-
diation, but undergo intermolecular anthracene-an- ture 209.905*u7p3"8 By this dissymmetrical mode of 4r
thracene c y c l ~ a d d i t i o n . ~ ~ ~ + 41r cycloaddition, spatial overcrowding in the pho-
toproducts due to interaction of the methyl groups and
the proximate aromatic hydrogen atoms is decreased.

The mechanism of photochemical intramolecular 4a

+ 4r cycloaddition of linked anthracenes, and that of
the photolytic cycloreversion, has been a subject of Excited-state properties of silyl-hinged biaanthracenes
considerable interest with respect to the involvement 204-207 in terms of reaction and fluorescencequantum
of excimers and biradicals as intermediate^.^^^^^^^ In yields are listed in Table IX. Significantly, photoex-
several electron spectroscopic studies on 1,2-di(9- cited silicon-linked bis-anthracenes 205-207 exhibit
anthryl)ethanes,evidence has been obtained for more both monomer fluorescence, i.e. emission from the
than one excimer geometry, and for the existence of locallyexcited state,and emission from an excimer state.
anti and gauche conformers.285~314*326~3m*331 Geometri- For anthryl-substituted disiloxane 205,the quantum
cally different excimers also have been detected spec- yield of excimer emission is remarkably high. It has
troscopically for photoexcited 1,2-di(l-anthryl)ethane been established in a detailed spectroscopic investi-
+
which undergoes intramolecular 4 r 4 s cycloaddition gation that isomerization by cycloaddition and fluo-
involving the 9,lO positions of both anthracene moi- rescence from the excimer state are competing pro-
eties.% The polar character of the excimer state of cesses, and the photoreactive excimer is suggested to
dianthrylethanes is borne out in the dependence of ita be characterized by unsymmetrical arrangement of
electronic structure on solvent polarity.326Moreover, overlapping anthracene ~-systems.~9
results obtained by time-resolved picosecond laser
spectroscopy indicate the formation of a common D. Anthrylalkyl Ethers
intermediate in the photochemical cycloaddition and
cycloreversion, and it has been established spectro- +
The intramolecular 4r 4 r cycloaddition of nu-
scopicallythat intramolecularelectron transfer between merous bichromophoric (9-anthry1)methylethers has
the two aromatic moieties is involved in both the been extensively investigated in conjunction with their
cycloaddition and cycloreversion p r o ~ e s s . 3 ~ ~ * 3 ~ potential use as photochromic material~.~~J~@2*-w
The effects of substituents on the excited state prop-
C. DimethylsllyCLinked Blchromophorlc erties of bis[(9-anthryl)methyl] ethers 21Oa-f in terms
of quantum yields of cycloaddition and fluorescence in
Anthracenes methylcyclohexane at room temperature are summa-
The effects of molecular geometry on the course of rized in Table X. Quantum yields of reaction range
unimolecular photochemistry of bichromophoric an- from an optimal value of 0.32 for the parent compound
thracenes are particularly evident in the excited-state 210a,to 0.16 for disubstituted 210f (R1= cyano; R2=
properties of bisanthracenes 204-207, in which sub- phenyl). Slightly higher cyclization quantum yields
Unhnolecular Photochemistry of Anthracenes Chemlcal Reviews, 1993, Vol. 93,No. 1 163

Table IX. Quantum Yields of Isomerization (h),

Monomer Fluorescence (Oh),and Excimer
Fluorescence (OpmC) for Silicon-Linked Bisanthracenes
compd @R cycloaddition
204 0.05 0.45 4r + 2r
206 0.13 0.02 0.13 dissymm4*+ 4r
206 0.002 0.03 0.02 dissy"4r + 4r
207 0.0008 0.085 0.025 dissymm4r+4r
212 213 21 4 21 5 210
Table X. Substituent Effects on the Quantum Yields of
Fluorescence (OF)and Isomerization by Cycloaddition
(*) of Bis[(9-anthryl)methyl] Ethers 210 in moieties, respectively.1es Intramolecular 4 r 4r +
Met hylcyclohexanem cycloaddition also characterizes the photochemistry of
210 R' R2 + b (9-anthryllmethyl ethers of (1-naphthy1)methanoland
of furfuryl alcoho1.3021351
By contrast, irradiation of (9-
a H H 0.03 0.32
b H CH3 0.07 0.32 anthryllmethyl ethers of (2-naphthyl)methanol, (9-
C H C6H5 0.09 0.19 phenanthryl)methanol, and (1-pyrenyl)methanol gave
d H Br 0.03 0.18 mixtures of intermolecularly formed head-to-head and
e CH3 CN 0.05 0.25 head-to-tail dimers involving only the anthracene
f C6H5 CN 0.05 0.16 r-~ystems.~~~
As for diastereomeric a,a'-disubstituted (9-anthry1)-
have been observed in a c e t ~ n i t r i l e .Fluorescence
~~ methyl ethers 217a,b and 218a,b,the meso form 217
quantum yields generally are <0.10. and d,l form 218 have been found to isomerize by 4 r

& 0 0
+ 4 r cycloaddition with equal quantum efficiency (a
= 0.25).366 However, the conformational differences

R-C-H R-C-H
I I
0 0
I I
R-F-H H-F-R

an-1
2 l l M ( R * 4Hs) b: n - 2
(we Table X )
217a-b 218a-b
Analogous to the 10,lO'-diphenyl derivative of 1,2-
di(9-anthry1)ethane 168 mentioned above (section VI- between the meso and d,l forms are borne out in their
ILB), photoexcited bis [( 10-phenyl-9-anthry1)methyll distinctly different fluorescence properties. The meso
ether (211a;n = 1) does not isomerize, but is charac- form, which may assume a conformationof fuUy eclipsed
terized by high fluorescence quantum yield of 0.55. More parallel aligned anthracene r-systems, was found to be
important, 21 la in fluid solution at room temperature nonfluorescent. By contrast, the d,l diastereomers in
exhibits both structured fluorescence, from the locally cyclohexane solution at room temperature are fluo-
excited state (a = 0.211, and red-shifted broad excimer rescent (a -0.01), and the emission derives mainly from
emission (a = 0.34), indicating geometrically favored an excimer state (Amm -480 nm). Since a sandwich
intramolecular interaction of overlapping anthracene arrangement of two anthracene moieties in the d,Z
moieties.360 The fluorescence properties of 211a are diastereomers 218 is precluded for structural reasons,
dependent on solvent viscosity and have been exploited the geometry of the luminescent excimer most likely is
in probing molecular motions in polymer^.^" characterized by only partially overlapping anthracene
Dual emission in solution at room temperature also r-system~.~~~~~~
characterizes the excited state properties of the bis- Some 9-anthryl (9-anthryllmethyl ethers have only
(10-phenyl-9-anthryl) ether 211b (n = 2). However, recently become available and were found to isomerize
extending the methyl ether linkage in 211a by an photochemically by way of rearrangement to give 10-
oxymethylene group markedly alters the kinetics of substituted 9-anthrones.m Thus, photoexcited 219 in
excimer formation. Thus, the quantum yield of excimer toluene solution disappears with a remarkably high
emission has decreased to 0.21, and emission from the quantum yield of 0.57. Preparative irradiations, carried
locally excited state of 211b is as high as 0.69.366 out in ethyl acetate solution with light of wavelengths
For the series of 9-anthryl-substituted ethers 212- > 400 nm, lead to anthrone derivatives 220 and 221 in
215,quantum yields for the photochemical isomeriza-
tion by 4 r + 4 r cycloaddition (ad and fluorescence
(&) have been determined. In general, the ether-linked
bis-anthracenes isomerize with higher quantum effi-
ciency than the correspondinga,w-di(9-anthryl)alkanes.
The (Qanthry1)methyl ether of (1-anthry1)methanol
(216) isomerizes with a quantum yield of 0.15 by
dissymmetrical 4u + 4 r cycloaddition involving the
9,lO and 1',4' positions of the 9-anthryl and 1-anthryl
164 Chemical Revlews, 1993, Vol. 93,No. 1

an approximate ratio of 4:l. In view of the CIDNP teristic of his compound.367In a comprehensive paper
evidence obtained for the photochemical homolytic published in two parts in 1868/1869,Fritzache proposed
@-cleavageof (9-ary1oxy)acetophenones(seesection IV), that his hydrocarbon C14H10, melting at 210-212 C,
the photochemical formation of the minor product 221 should be called photene (Photen).38eFor another
by an analogous radical mechanism appears probable. hydrocarbon, of somewhat lower melting point (196 C),
As for the major product, namely,anthronyl-substituted but very similar photochemical properties, he proposed
dihydroanthracene derivative 220,another conceivable the name phosene (Phosen), to indicate both their
pathway may involve an intramolecular 4a + 4a behavior towards light, and their close relationship.
cycloaddition of 219, leading to an oxymethylene For the photoproducts of photene and phosene,
annelated dianthracene. Cleavage of the oxetane Fritzsche suggested the names paraphotene and para-
moiety in a thermal reaction would account for the phosene, respectively, and he had some experimental
observed product 220. evidenceto presume that paraphoeenemaybe is formed
Indications for the involvement of a cycloaddition from two molecules of phosene, and heat only halves
step in the migratory rearrangement of 9-anthryloxy paraphosene (peut-&tre,le paraphdne serait-il form6
compounds to 9-anthrones has been obtained in an par deux molbcules de phoshe, et la chaleur ne fabait-
investigation of the trichromophoric anthracene 222, elle que dbdoubler le paraphos~nem).38eb*m Fritzsche
which isomerizes with a quantum yield of 0.16.% For also remarked on a light-sensitive impurity he named
222, there are two intramolecular 4a + 4a cycloaddition Chrysogen, which caused the yellow color of crude
reactions possible, and two isomeric photoprodudshave photene.
been isolated. Photoisomer 224 deriving by intramo- As for artificially prepared anthracene, Fritzsche
lecular 47r + 4a cycloaddition of the cis-dianthryleth- found the samplea he had obtained from his revered
ylene moiety in 222 is formed in only 13% yield. The friend Limpricht, and from Messrs. GrHbe and
major product, isolated in 67% yield, is the allene Liebermannto be photene, contaminated by a small
derivative 223. Ita stereochemistry about the allene amount of phosene. Fritzsche also checked a sample
moiety indeed is such as to have the methoxy group of Berthelots anthracene, and proclaimed it to be pure
and the 9-anthronyl moiety cis oriented, as would be photene. This belated and seemingly obstinate claim
expected from either a concerted rearrangement of 222, to the name photene may seem remarkable, but
or from ring opening of a thermally labile oxetane should be seen in light of the significance which
intermediate. anthracene had gained in 1868by ita preparation from
alizarin.386 The discovery of the synthesis of alizarin
h
from anthracene only one year later, when the structure
of anthracene was still unknown, was to become the
m foundation of a chemical ind~stry.~~O
Concerning phosene, Barbier in 1874concluded from
I
...
hv
+ a reinvestigation that it was a mixture of anthracene
0
and phenanthrene, which in 1872, the year after
Fritzsches death, had been discovered in crude
a n t h r a ~ e n e ? ~ Since
l-~~~ phenanthrene does not dimer-
ize upon irradiation, Fritzsches paraphoeene thus
0
must have been dianthracene.
223 Ironically, the proposal of the correct structure of
dianthracene (2) by Orndorff and Cameron in 1895 is
I X . Retrospective Contemplatbns and based on their assumption that anthracene existed in
Conclusions cis and trans stereoisomeric forms 22Sa/22Sb.6 Arm-
strongs correct anthracene structure 226 of 1890,
In the realm of organic photochemistry, Fritzsches wherein C is the nucleus of benzene, was rejected
name is intimately associated with the dimerization of because it did not represent the chemical conduct of
anthracene.= However, Fritzsche himself emphatically anthracene.
rejected the idea that the hydrocarbon, which he had
isolated from coal tar about 10years before he described H

ita peculiar behavior towards sunlight, and which he

had left unnamed, should be called a n t h r a ~ e n e . ~ l ~ ~ ~ * ~
He was aware of paranaphthaline, melting around
*@@ H

180 C,which Dumas and Laurent in 1832had isolated

from coal tar and which Laurent in 1837 had named
anthracdne.381*382 Fritzsche also knew the paper on To paraphrase Armstrong, such speculations, even
anthracene or paranaphthaline, which Anderson in if proved to be entirely false, at least served to suggest
Glasgow had published in l86LS3 Anderson and his fresh lines of experimental inquiry, and on this account
contemporaries active in the area of hydrocarbon were not ody permissible but also d ~ i r a b l e In
. ~1920,
~
chemistry, namely, Limpricht in Greifswald, Berthelot by comparison of refraction measurements on a sub-
in Paris, and Graebe and Liebermann in Berlin, all stituted anthracene and its 9,lO-dihydroderivative, von
considered Fritzsches hydrocarbon and anthracene to Auwers ruled out the commonly accepted 9,lO-bridged
be identical, though none of them ever noted ita anthracene structure, and confirmed Armstrongs
sensitivity toward light.%-% Fritzsche, by contrast, quinoidstructure 226.37sNevertheless, as late as 1966,
considered the photochemical properties and the flu- C.K.Ingold argued that the pecularities of anthracene
orescence, which he discussed in detail, to be charac- chemistry could not be explained away by double bond
Unkndecular Photochemistry of Anthracenes Chembl Reviews, lQQ3,Vol. 93,No. 1 186

conjugation without bridged structures", and that "the (20) Co&n,C. A.;Orgel,L. E.;Taylor, W.; Weh, J.The&~ctureand
ultraviolet spectrum of dianthracene. J. Chem. SOC.1966,2981-
9:lO-bridge must be of outstanding importance in 2962.
anthra~ene".~"~ The problem of "bridged anthracene" (21) Creene, F. D.; Misrock, S. L.; Wolfe, J. R. The rtructure of
was finally settled in 1982,when Pritschins and Grimme anthracene photodimers. J.Am. Chem. Soc. 1966,77,3862-W.
(22) Greene, F. D.; Ocampo, S.R.; Kaminaki, L. A. The acid-catalyzed
accomplished the synthesis of 9,lO-Dewaranthracene.'& dimxiation of bis-9-anthraldehyde. J. Am. Chem. SOC. 1967,79,
Chrysogen, the yellow trace impurity in anthracene, 5967-6962.
which Fritzsche had found to undergo "a similar light- (23) Applequiet, D. E.; Litle, R. L.; Friedrich, E. C.; Wall, R. E.
Anthracene photodimera. I. Eliminationand substitution reactiom
induced transformation as photene and phosene" of the photodimer of 9-bromoanthracene. J.Am. Chem. SOC.1969,
deserves a ~ o m m e n t . ' * ~ *Its
~ ~structure
' remained a 81,462-466.
(24) Applequiet, D. E.; Friedrich, E. C.; Rogers, M. T. Anthracene
mystery until 1934, when the chromatographic sepa- photodimers. II. The electric momenta and structures of the
ration of chrysogen from anthracenewas accomplished photodimers of 9-haloanthracenes. J. Am. Chem. Soc. 1969,81,
in connection with cancer research. Chrysogen turned 457-468.
(26) Applequiet, D. E.; Brown, T. L.; Kleiman, J. P.; Young, S. T.
out to be identical with naphthacene ( t e t r a ~ e n e )As .~~~ Structures of the photodimere of Banthroic acid, methyl 9-an-
a vindication of Fritzsche's original observations, the throate, and 9-anthraldehyde. Chem. 2nd. 1969,860-851.
blue fluorescence of crystalline anthracene was found (26) Lalande, R.; Calas, R.; Bouas-Laurent, H.C. R. Sbances Acad. Sci.
1969,249,706-707.
to be "nearly totally quenched by addition of (27) Calas, R.; Lalande, R. Bull. SOC. Chim. Fr. 1069,763-766.
1/100 OOO% " of naphthacene. The phenomenon of (28) Lalande, R.; Calm, R. Bull. SOC. Chim. Fr. 1969,766-770.
(29) Calm, R.; Lalande, R. Bull. SOC. Chim. Fr. 1969,770-772.
energy transfer in crystalline anthracene and "an- (30)Lalande, R.; Calas, R. Bull. SOC. Chim. Fr. 1960,144-147.
thracene-type" hydrocarbons containing small amounts (31) Calas, R.; Lalande, R.; Mauret, P. Bull. SOC. Chim. k.1960,148-
of naphthacene was to be investigated in 1940 by 149.
(32) Greene, F. D. Problems of stereochemistry in photochemical
Weigert, whose first fundamental contribution to the reactions in the anthracene area. Bull. SOC. Chim. k.1960,1366-
photochemistry of anthracene had been published 35 1360.
years e ~ l i e r . As
~ ?for
~ the
~ ~ photochemical properties (33) Vember, T. M.; Kiyanekaya, L. A.; Cherkasov, A. S. Relative
velocities of Dhotochemid conversions of anthracene derivativea.
of naphthacene, they are indeed similar to those of Zh. ObshchKhim. 1963,33,2342-234% J. Gen.Chem. USSR (Engl.
anthracene, and they are still being !hMl.) 1963, 33,2281-2286.
Perusal of the recent literature suggests that the (34) Bow-Laurent, H. Thesis, Faculte des S c i e n a , Bordeaux, 1964.
(36) Calas,R.;Lalande,R.;Faugere,J.-G.;Moulines,F.Bull.Soc.Chim.
anthracene chromophore will continue to play a prom- Fr. 1966.119-120.
inent role in the development of organic photochem- (36) Calan, R:;Lalande, R.; Mauret, P.; Moulines, F. Bull. SOC. Chim.
istry. The anthracene ?r-system remains to be a most Fr. 1966,121-123.
(37) (a) Bowen, E. J. The photochemistry of aromatic hydrocarbon
useful auxiliary, be it in probing the photochemistry in solutions. Advances in Photochemistry; Noyes, W. A., Jr., Ham-
micelles or c y c l o d e ~ t r i n sin
, ~structural
~~ studies on mond, G. s., Pitta, J. N., Jr., Eds.; Interscience Publishers: New
York, 1963; Vol. 1,pp 23-42. (b) Saltiel, J. The m e c h " of some
lipid membranes,% or the investigation of energy photochemical reactions of organic molecules. Survey Ron.
transfer in DNA.389 Numerous new anthracene deriv- Chem.; Scott, A. F., Ed.; Academic Prese: New York,1963;Vol. 1,
atives of potential photochemical and photophysical pp 23-42.
(38) Vember,T. M. Quenching of the fluorescenceof meeodieubtituted
interest are being synthesized.*= Their investigation anthracene derivatives by anthracene, and the formation of mixed
by sophisticated experimental techniques should lead photodimers. Opt. Spektrosk. 1966,20,347-349; Opt. Spectmc.
to a better understanding of excited-state reactions. (Engl. Transl.) 1966,20,188-190.
(39) Wei, K. S.;Livingston, R. Reversible photodiierization of an-
thracene and tetracene. Photochem. Photobiol. 1967,6,229-232.
(40)Lapouyade,R.; C a n t e l l a n , A . ; B o w - L , H. CP. Slances Acad.
X. References Sci. 1969,268, 217-219.
(41) Bow-Laurent, H.; Lapouyade, R. Croeeed photodimeriaation in
Foreign language article titles are not included in the solution between donor and acceptor anthracenic monomers. J.
references. Chem. SOC., Chem. Commun. 1969,817-818.
(42) Bowen, E. J.; Rohatgi, K. K. Photochemistry of anthracene. Part
Fritzeche, J. Bull. Acad. Zmper. Sci. St.-Pbtersbourg 1866,9,406- 11. The photochemical reaction of anthracene with carbon ktra-
419; 2. Chem. 1866,9 (N.F. 21, 139-144. chloride. Dkcws. Faraday SOC. 1953,14,146-160.
Fritzeche, J. Bull. Acad. Zmper. Sci. St.-Phtersbourg 1867,11,385- (43) Bowen, E. J.; Tanner, D. W. The photochemistry of anthracenes.
397; J. Prakt. Chem. 1867,101,333-343; 2.Chem. 1867,lO (N.F. Part 3. Inter-relations between fluorescence quenching, dimer-
3), 289-294. ization, and photo-oxidation. Trans. Faraday SOC. 1966,51,476-
Elbs, K. J. Prakt. Chem. 1891,44,467-469. 481.
Linebarger, C. E. On the preparation and constitution of para- (44) Bowen, E. J.; Sahu, J. The effect of temperature on fluorescence
anthracene. Am. Chem. J. 1892,14,697-602. of solutione. J. Phys. Chem. 1969,63,4-7.
Omdorff, W. R.; Cameron, F. K. Paranthracene or dianthracene: (46) Medinger, T.; Wilkinson, F. Mechanism of fluorescencequenching
A polymeric modification of anthracene. Am. Chem. J. 1896,17, in solution. Part 1. - Quenching by bromobenzene. Trans.
668-681. Faraday SOC. 1966,61,620-630.
(a) Luther, R.; Weigert, F. 2.Phys. Chem. 1906,51,297-328. (b) (46) Parker, C.A.; Joyce, T. A. Determination of triplet formation by
Luther, R.; Weigert, F. 2.Phys. Chem. 1906,53,386-427. the measurement of sensitized delayed fluorescence. Trans.
Bodenstein, M. 2.Phys. Chem. 1913,85, 329-397. Faraday SOC. 1966,62,2786-2792.
Volmer, M. Ann. Phy8. 1913,40, 776-796. (47) Kellogg, R. E. Second triplet state of anthracene. J.Chem. Phys.
Weigert, F.; Knjger, 0.2. Phy8. Chem. 1913,85, 679-622. 1966,44,411-412.
Weigert, F.; Kummerer, L. Ber. Dtsch. Chem. Ges. 1914,47,89& (48) Bennett, R. G.; McCartin, P. J. Radiationlea deactivation of the
908. fluorescent state of substituted anthracenes. J.Chem. Phys. 1986,
Volmer, M.; Riggert, K. 2.Phys. Chem. 1922,100,602-511. 44,196*1972.
Taylor, H. A.; Lewis, W. C. M. Studies in chemical reactivity. 11. (49) Horroch, A. R.; Wi1khn;F. Triplet state formation efficienciea
The a n t h r a c e n e - d h t h n e reactions, photochemical and ther- of aromatic hydrocarbons in solution. Roc. R. Soc. London, Ser.
mal. J. Am. Chem. SOC. 1924,46, 1606-1615. A 1968,306,257-273.
Capper, N. S.; Marsh, J. K. Light absorption and emhion (60)Stevens, B. Photoaeeociation in aromatic system. Aduances in
phenomena in anthracene. J. Am. Chem. SOC. 1926, 47, 2848- Photochemistry; Pitte, J. N., Jr., Hammond, C. S.,Noyes, W. A.,
2850. Jr., Eda.; Interscience: New York, 1971; Vol. 8, pp 161-226.
Weigert, F. Naturwbsenschaften 1927,15, 124-126. (61) Cowan, D. 0.;Schmiegel, W. W. Photodimerization of Qanthroic
Weigert, F.; Pruckner, F. 2. Phys. Chem., Ergtinzungsband: acid and sodium 9-anthroate. J . Am. Chem. SOC. 1972,W, 6779-
Bodenstein-Festband, 1931, 776-784. 6788.
Suzuki, M.; Volmer, M. Naturwissenschaften 1936,23, 197. (62) Shon,R. S.-L.; Cowan, D. 0.;Schmiegel,W. W.P h o t o d i e h t i o n
Suzuki, M. Bull. Chem. SOC. Jpn. 1943,18, 146-166. of Santhroate esters and 9-anthramide. J. Phys. Chem. 1971,79,
Suzuki, M. Bull. Chem. SOC. Jpn. 1949,22,172-178. 2087-2092.
Suzuki, M. Bull. Chem. Soc. Jpn. 1960, 23,120-124. (63) Cantellan, A. C.R. Sbances Acad. Sci. 1976,281, 221-224.
166 Chemlcal Reviews, 1993, Vol. 93, No. 1 Becker

(54)Castellan, A.; Lapouyade, R.;Bouas-Laurent, H. Bull. SOC. Chim. (84) Rice,J.;McDonald,D.B.;Ng,L.-K.;Yang,N.C.Effectofkity

Fr. 1976, 201-209. on fluorescence of anthracenes in solution. J. Chem. Phys. 1980,
(55) Castellan, A.; Lapouyade, R.; Bouas-Laurent, H.; Lallemand, J. Y. 73, 4144-4146.
Head-bhead mixed photodimers between monomesosubstituted (85) Heldt, J. R. Influence of internal heavy atom on the spectroscopic
anthracenes; control of photocycloaddition selectivity by charge- properties of 9-acetoxy-10-phenylanthracenederivatiwa 2.Natur-
transfer and dipole-dipole interactions. Tetrahedron Lett. 1975, forsch. 1984,39a, 952-959.
2467-2470. (86)Werner, T. C.; Rodgers, J. Studies on the fluoreecenceproperties
(56) Cowan. D. 0.; Drisko, R. L. Photochemical techniques and the of me-so-substituted amidoanthracenes. J. Photochem. 1986,32,
photdimerization ofanthraceneand related compounds. Elements 59-68.
oforganicphotochemistry;Plenum Prese: New York, 1976;Chapter (87) UhmannsrBben, H.-G.; Heldt, J. R.; Heldt, J. Tripletstate related
2. photophysical properties of 9-acetoxy-10-phenylanthracenede-
Schnepp, 0.;Levy,M. Intramolecular energy transfer in a naph- rivatives. J. Photochem. Photobiol. A: Chem. 1990,51,207-214.
thalene-anthracene system. J.Am. Chem. SOC. 1962,84,172-177. (88)Cuilbault, C. G., Ed. Practical Fluorescence; 2nd ed.; Marcel
Lett, S. A.; Cheung, H. T.; Blout, E. F. Energy transfer. A system Dekker: New York, 1990.
with relatively fixed donor-acceptor separation. J.Am. Chem.SOC. (89) Lukace, J.; Lampert, R. A.; Metcalfe, J.; Phillip, D. Photophysice
1965,87, 995-1003. of substituted anthracenes wed as chemiluminescenceactivators.
h u h , R. D.; Evans, T. R.; Leermakers, P. A. Intramolecular J. Photochem. Photobiol. A: Chem. 1992,63,69-65.
electronic energy transfer in some indole alkaloids and related (90)Brotin, T.; Waluk, J.; Desvergne,J.-P.; Bow-Laurent, H.; Michl,
donor-acceptor systems. J.Am. Chem. SOC. 1968,90,6897-6904. J. Electronic abeorption properties of symmetrical dialkoxyan-
Applequist, D. E.; Searle, R. Synthesis, brominolysis,and pyrolysis thracenes. Linear dichroism and magnetic circular dichroism. J.
of a "Dewar" anthracene. A free radical displacement on carbon. Photochem. Photobiol. 1992,55, 335-347.
J. Am. Chem. SOC. 1964,86, 1389-1391. (91) Brotin, T.; Desvergne, J.-P.; Fages, F.; UtermWen, R.;Bonneau,
Weinshenker, N. M.; Greene, F. D. 9,9'-Didehydrodianthracene.J. R.; Bow-Laurent, H. Photcmtationary fluorescence emkion and
Am. Chem. SOC. 1968,90, 506. time resolved spectroscopy of symmetrically disubetituted an-
Viavattene, R. L.; Greene, F. D.; Cheung, L. D.; Majeste, R.; thracenes on the meso and side ring: The unusual behavior of the
Trefonaa,L. M. 9,Y,lO,lO'-Tetradehydrodianthracene. Formation, 1,rl-derivative. Photochem. Photobiol. 1992,55, 349-368.
protection and regeneration of a strained double bond. J. Am. (92) Hirayama, S. Effect of substituent on the behaviour of the excited
Chem. SOC. 1974, 96,4342-4343. singlet and triplet statee in carbonyl derivatives of anthracene of
Froehlich, P.; Wehry, E. L. The study of excited-state complexes the type 9-X-CO-A. J. Chem. SOC.,Faraday Trans. 1 1982,2411-
('exciplexes") by fluorescence spectroscopy. In Modern Fluores- 2421.
cence Spectroscopy; Wehry, E. L., Ed.; Plenum: New York, 1976; (93) Lewis, C.; Ware, W. R. Wavelength effects in fluorescence quench-
Vol. 2, pp 319-438. ing: The anthracen - carbon tetrachloride system. Chem. Phys.
Rattig, W.; Majenz, W.; Lapouyade, R.; Vogel, M. Adiabatic Lett. 1972, 15, 290-292.
photochemistry with luminescent producte. J. Photochem. Pho- (94) Jones, R. N. The influence of restrided rotation on the absorption
tobiol. A: Chem. 1992,65,95-110. spectra of aryl Substituted aromatic hydrocarbons. J. Am. Chem.
Becker, H.-D. Excited state reactivity and molecular topology Soc. 1941,63, 1658-1661.
relationships in chromophorically substituted anthracenes. Ad- (95) Guetav, K. Molecular geometry and excited electronic states. Part
vances in Photochemistry; Volman, D. H., Hammond, G. s., XIII. Conformational geometries of 9,lO-diphenylanthracene in
Gollnick, K., Eds.; Interscience Publishers: New York, 1990;Vol. different electronic statee and ita electronic spectral behavior. J.
15, pp 139-227. Mol. Struct. (Theochem) 1964,110,219-228.
Mazzucato, U.; Momicchioli, F. Rotational isomerism in trans- (96)Werst,D.W.;Gentry,W.R.;Barbara,P.F.The&andSItorsiod
1,2-diarylethylenes. Chem. Rev. 1991, 91, 1679-1719. potentials of 9-phenylanthracene. J. Phys. Chem. 1966,89,729-
Desvergne, J.-P.; Bow-Laurent, H. Cycloaddition reactions in- 732.
volving 4n electrons: (4+4) cycloaddition reactions between (97) Werst,D.W.;Londo,W.F.;Smith,J.L.;Barbara,P.F.Theexcited
unsaturated conjugated systems. In Photochromism: Molecules state torsional potentials of substituted 9-phenylanthracenes.
and Systems; Diur, H., Bouas-Laurent, H. Eds.; Elsevier: Am- Chem. Phys. Lett. 1986,118,367-374.
sterdam, 1990;Chapter 14, pp 561-630. (98) Werst, D. W.; Brearley, A. M.; Gentry, W. R.; Barbara, P. F. SI
FBrster, Th. Fluoreszenz organischer Verbindungen; Vandenhcek Torsional potentials of substituted anthracenes. J. Am. Chem.
& Ruprecht: GBttingen, 1951. SOC. 1987,109,32-40.
Jaff6, H. H.; Orchin, M. Theory and Applications of Ultraviolet (99)Becker, H.-D.; Langer, V.; Sieler, J.; Becker, H.-C. Molecular
Spectroscopy; John Wiley and Sons, Inc.: New York, 1962. conformations of g,Y-bianthryl, di-9-anthrylmethane, and some
Clar, E. Polycyclic Hydrocarbons; Academic Press; London related twisted anthracene derivatives. J. Org. Chem. 1992,57,
(Springer-Verlag: Berlin-G6ttingen-Heidelberg), 1964; Vol. 1, 1883-1887.
Chapters 5-9, pp 24-104. (100) Becker, H.-D.; Sandros, K.; H a " , L.Excited state properties of
Calved, J. G.; Pitts, J. N., Jr. Photochemistry, John Wiley & Sons, cis- and trans-l,2-di(9-anthryl)ethylenes.J. Org. Chem. 1981,46,
821-823.
Inc.: New York, 1966. (101) Becker, H.-D. On the relationship between molecular geometry
Turro, N. J. Modern Molecular Photochemistry; The Benjamin/ and excited state reactivity. Adiabatic photoreactions involving
Cummings Publ. Company, Inc.: Menlo Park, CA, 1978. anthracenes. Pure Appl. Chem. 1982,54,1589-1604.
Birks, J. B.; Appleyard, J. H.; Pope, R. The photodimers of (102) Becker,H.-D.; Anderseon,K.Ontherelatiomhipbetweenmolecular
anthracene,tetracene and pentacene. Photochem. Photobiol. 1963, geometry and excited-state properties of g-anthrylekenes, J.Org.
2,493-495. Chem. 1983,48,4542-4549.
Jones, R. N. Some factors influencing the ultraviolet absorption (103) Becker, H.-D.; Patrick, V. A.; White, A. H. Molecular geometry of
spectra of polynuclear aromatic compounds. I. A general survey. (E)-and (Z)-B@-styryl)anthracenes.Aut. J.Chem. 1964,37,2215-
J. Am. Chem. SOC. 1945,67, 2127-2150. 2224.
(75) Bouas-Laurent, H.; Lapouyade, R.Bull. SOC. Chim.Fr. 1969,4250- (104) Becker,H.-D.;Engelhardt,L.M.;Hansen,L.;Patrick,V.A.;White,
4258. A. H. On the molecular structure of (E)-1,2-di(Banthryl)ethene.
. . Mauldinn. D. R.: Roberts. B. G. Electronic absorotion and
(76) X-ray structure analysis of the parent compound and ita 10,lW-
fluoresce&e of phenylethynyl-substituted acenes. J.drg. Chem. dibromo derivative. A u t . J. Chem. 1964,37, 1329-1335.
1969,34, 1734-1736. (105) Becker, H.-D.; Hansen, L.; Skelton, B. W.; White, A. H.
(77) Birks, J. B. Photophysics of Aromatic Molecules; Wiley-Inter- ((E)-l-(BAnthryl)-2-(lO-methyl-9-anthry Molecularstruc-
science: London, 1970. ture and spectroscopic properties. Aust. J. Chem. 198(i,38,809-
(78) Berlman, I. B. Handbook of Fluorescence Spectra of Aromatic 815.
Molecules, 2nd ed.; Academic Press: New York, 1971. (106) Castel, N.; Fiacher, E.; Bartocci, G.; Maeetti, F.; Mazzucato, U.
(79) Michl, J.; Thulatrup, E. W.; Eggers, J. H. Polarization spectra in Viscosity-induced emission anomalies in 1,2-diarylethyleneeand
stretched polymer sheets. V. Excited states of anthracene and in distyrylbenzenes and -naphthalenes. J. Chem. SOC., Perkin
transition moment directions in aminoanthracenes. Ber. Bunsen- Trans. 2 1986, 1969-1975.
Ges. Phys. Chem. 1974, 78,575-586. (107) Bhattacharyya, K.; Chattopadhyay, S.K.; Bard-Tosh, S.;Das, P.
(80)Werner, T. C. Use of fluorescence to study structural changes and K. Excited-state properties of trans-(9-anthryl)ethylenes.JWects
solvation phenomena on electronically excited molecules. In of geometric distortion about single bond. J. Phys. Chem. 1986,
Modern Fluorescence Spectroscopy; Wehry, E. L., Ed.; Plenum: 90,2646-2651.
New York, 1976; Vol. 2, pp 277-317. (108) Becker,H.-D.;Anderaeon,K.Ontherelationehipbetweenmolecular
(81) Schoof, S.;Ghten, H.; von Sonntag, C. Ber. Bunsen-Gee. Phys. geometry and photochemical properties of l,2-substituted 1,2-di-
Chem. 1977.81.305-309. Banthrylethylenes. J. Org. Chem. 1987,52,6205-5213.
(82) Schoof, S.; Gtisbn, H.; von Sonntag, C. Ber. Bunsen-Ces. Phys. (109) Becker, H.-D.; Hansen, L.; Skelton, B. W.; White, A. H. Molecular
Chem. 1978,82, 1068-1073. topology of l,2-substituted (E)- and (2)-1,2-di(g-anthryl)ethenee.
(83) Dreeskamp, H.; Pabst, J. Thermally assisted and heavy atom A u t . J. Chem. 1988,41, 1557-1569.
assisted intersystem crossing in mebsubstituted anthracenes. (110) Becker,H.-D.;Sandros,K. Ontherelationehipbetween fluorescence
Chem. Phys. Lett. 1979,61, 262-265. and moleculargeometry. Solvent-aeeistedformation of lumineamnt
Unimokular Photochemistry of Anthracenes Chemical Reviews, 1993, Vol. 93, No. 1 167

intramolecular exciplexesfrom anthronyl-substituted anthracenes. (134) Akkaya, E. U.; Huston, M. E.; Czarnik, A. W. Chelation-enhanced
Chem. Phys. Lett. 1978,53, 228-231. fluorescence of anthrylazamacrocycle conjugate probes in aqueous
(111) Becker, H.-D.; Sandros, K. On the relationship between fluorescence solution. J. Am. Chem. SOC.1990,112,3590-3593.
and molecular geometry. Formation of a luminescent intramo- (135) (a) de Silva, A. P.; Sandanayake, K. R. A. S. Fluorescence 'off-on"
lecular anthracene-ethylene exciples by electronic excitation of signalling upon linear recognition and binding of a,@-alkanediyl-
lepidopterene. Chem. Phys. Lett. 1978,55, 498-402. diammonium ions by 9,10-bis[(l-aza-4,7,10,13,16-~ntao~cycl~-
(112) Becker, H.-D.; Andemon, K.; Sandros, K. Stannous chloride tadecy1)lanthracene. Angew. Chem.,lnt.Ed. Engl. 1990,29,1173-
mediated formation of (9anthryl)methyl dimers from (halogenom- 1175. (b)Bissell,R.A.;deSilva,A.P.;Gunaratne,H.Q. N.;Lynch,
ethyhnthracenes. Ground-state and excited state reversibility of P. L. M.; Maguire, G. E. M.; Sandanayake, K. R. A. S. Molecular
intramolecular [4+21 cycloadditions. J. Org. Chem. 1980,45,4549- fluorescent signalling with 'fluor-spacer-receptor' systems: Ap-
4555. proaches to sensing and switching devices via supramolecular
(113) Becker, H.-D.; Sandros,K.; Andemon, K. Adiabatic photoreactions photophysics. Chem. SOC.Reu. 1992,21, 187-195.
involving anthracenes. Intramolecular exciplex formation by (136) de Silva, A. P.; Gunaratne, H. Q. N.; Sandanayake, K. R. A. S. A
photolytic cycloreversion. Chem. Phys. Lett. 1981, 77, 246-252. new benzo-annelated cryptand and a derivative with alkali cation-
(114) Ferguson, J.; Robbins, R. J.; Wilson, G. J. Photophyaics and sensitive fluorescence. Tetrahedron Lett. 1990,31, 5193-5196.
photochemistry of coupled chromophores: Lepidopterene and ita (137) (a) de Silva, A. P.; Gunaratne, H. Q. N. Fluorescent PET (photo-
dimethyl derivative. J. Phys. Chem. 1984,88,5193-5197. induced electron transfer) sensors selective for submicromolar
(115) Ferguson, J.; Robbins, R. J.; Wilson, G. J. Photophysics and calcium with quantitatively predictable spectral and ion-binding
photochemistry of lepidopterene: Ground-state procease. J.Phys. properties. J. Chem. Soc., Chem. Commun. 1990, 186-188. (b)
Chem. 1986, 90,4222-4224. Bissell, R. A.; Calle, E.; de Silva, A. P.; de Silva, S.A.; Gunaratne,
(116) Creech, H. J.; Jones, R. N. The conjugation of horse serum abumin H. Q. N.; Habib-Jiwan, J.-L.; Peiris, S. L. A.; Rupasinghe, R. A. D.
with isocyanates of certain polynuclear aromatic hydrocarbons. J. D.; Samarasinghe, T. K. S. T.; Sandanayake, K. R. A. S.;Soumillon,
Am. Chem. Soc. 1941,63, 1661-1669. J.-P. Luminescence and Charge Transfer. Part 2. Aminomethyl
(117) Yoshida, T.; Uetake, A.; Murayama, H. Fluorescent labelling of anthracene derivatives as fluorescent PET (photoinduced electron
amino acids with 9-anthryldiazomethane and ita applications to transfer) sensorsfor protons. J.Chem. Soc.,Perkin Trans.2,1992,
high-performance liquid chromatography. J. Chromatogr. 1985, 1559-1564.
349,425-429. (138) Yoon, J.; Czarnick, A. W. Fluorescent chemosensors of carbohy-
(118) Goto, J.; Ito, M.; Katauki, S.; Saito, N.; Nambara, T. Sensitive drates. A means of chemicallycommunicating the binding of polyola
derivatization reagenta for optical resolution of carboxylic acids by in water based on chelation-enhanced quenching. J. Am. Chem.
HPLC with fluorescence detection. J. Li9. Chromatogr. 1986,9, SOC.1992, 114, 5874-5875.
683-694. (139) (a) Bouas-Laurent, H.; Desvergne, J.-P.; Fages, F.; Marsau, P.
(119) Roach,M. C.;Ungar,L. W.;Zare,R. N.;Reimer,L. M.;Pompliano, Anthraceno-crown ethers and cryptands. Cation-directed photo-
D. L.; Frost, J. W. Fluorescencedetection of alkylphosphonic acids physics and photochemistry. In Frontiers in Supramolecular
using p-(9-anthroyloxy)phenacyl bromide. Anal. Chem. 1987,59, Organic Chemistry and Photochemistry; Schneider, H.-J., Diirr,
1056-1059. H., Eds.; VCH Verlagsgesellachaft: Weinheim, 1991, pp 265-286.
(120) Bayliss, M. A. J.; Homer, R. B.; Shepherd, M. J. Anthracene-9- (b) Desvergne, J.-P.; Fages, F.; Bouas-Laurent, H.; Mmau, P.
carbonyl chloride as a fluorescence and ultraviolet derivatising Tunable photoresponsive supramolecular systems. Pure Appl.
reagent for the HPLC analysis of hydroxy compounds. J. Chro- Chem. 1992.64. 1231-1238.
matogr. 1988,445, 393-402. (140) Pritachins, W.; Grimme, W. 9,lO-Dewar-anthracene. Tetrahedron
(121) Faulkner, A. J.; Veening, H.; Becker, H.-D. O-(O-Anthryl)ethyl Lett. 1982,23, 1151-1154.
chloroformate: A precolumn derivatizing reagent for polyamines (141) Yang, N.-C.; Carr, R. V.; Li, E.; McVey, J. K.; Rice, S. A. 2,3-
determined by LC and fluorescence detection. Anal. Chem. 1991, Naphtho-2,5-bicyclo[2.2.0lhexadiene.J.Am. Chem. SOC.1974,W,
63, 292-296. 2297-2298.
(122) Hermann, U.; Tirmmler, B.; Maass, G.; Mew, P. K. T.; Vbgtle, F. (142) Carr, R. V.; Kim, B.; McVey, J. K.; Yang, N. C.; Gerhartz, W.;
Anthracenoyl crown ethers and cryptands as fluorescent probes Michl, J. Photochemistry and photophysics of 1,4-Dewarnaph-
for solid-phase transitions of phosphatidylcholines: Syntheses and thalene. Chem. Phys. Lett. 1976, 39,5740.
phospholipid membrane studies. Biochemistry, 1984, 23, 4059- (143) Michl, J. The role of biradicaloid geometries in organic photo-
4067. chemistry. Photochem. Photobiol. 1977,25, 141-154.
(123) de Silva, A. P.; Rupasinghe, R. A. D. D. A new class of fluorescent (144) Turro, N. J.; McVey, J.; Ramamurthy, V.; Lechtken, P. Adiabatic
pH indicators based on photo-induced electron transfer. J. Chem. photoreactionsof organic molecules. Angew. ChemJnt. Ed. Engl.
Soc., Chem. Commun. 1985, 1669-1670. 1979,18,572-586.
(124) P. Konopelski, J. P.; Kotzyba-Hibert, F.; Lehn, J.-M.; Desvergne, (145) Hart, H.; Ruge, B. Decamethylanthracene and ita g,lO-'Dewar"
J.-P.; Fages, F.; Castellan, A.; Bouas-Laurent, H. Synthesis, cation isomer. Tetrahedron Lett. 1977, 3143-3146.
binding, and photophyaical properties of macrobicyclicanthraceno- (146) Dickerman, S. C.; Berg, J. H.; Haase, J. R.; Varma, R. Crowded
cryptands. J. Chem. SOC.,Chem. Commun. 1985,433-436. anthracenes. I. 1,4,5&Tetraphenyl- and 1,4-diphenyl-S,lO-di-
(125) de Silva, A. P.; de Silva, S.A. Fluorescent signalling crown ethers; methylene-9,lO-dihydroanthracene.J. Am. Chem. SOC. 1967,89,
'switching on' of fluorescence by alkali metal ion recognition and 5457-5458.
binding insitu. J. Chem. Soc., Chem. Commun.1986,1709-1710. (147) Dickerman, S.C.; Haase, J. R. Crowded Anthracenes. 11. Meth-
(126) Guinand, G.; Marsau, P.; Lehn, J.-M.; Kotzyba-Hibert, F.; Konopel- ylene-methylarene tautomerism and long-range magnetic shielding
ski, J. P.; Desvergne, J. P.; Fages, F.; Castellan, A,; Bouas-Laurent, in 1,4,5,&tetraphenyl-9,lO-dmethylanthracene.J.Am. Chem.SOC.
H. Structures of two trichromophoric anthraceno cryptands. Acta 1967,89, 5458-5459.
Crystallogr. 1986, C42, 715-719. (148) Bowden, B. F.; Cameron, D. W. Stable hydrocarbon analogues of
(127) Bouas-Laurent, H.; Castellan, A.; Daney, M.; Desvergne, J.-P.; 9-anthrone: Methyl substituted 9-alkylidene-9,lO-dihydroan-
Guinand, G.; Marsau, P.; Riffaud, M.-H. Cation-directed photo- thracenes. J. Chem. SOC.,Chem. Commun. 1977, 78-79.
chemistry of an anthraceno-crown ether. J.Am. Chem. SOC.1986, (149) Clar, E. Chem. Ber. 1949,82, 495-514.
108, 315-317. (150) Meador, M. A.; Hart, H. Substituent effects on the photoisomer-
(128) Huston, M. E.; Haider, K. W.; Czarnik, A. W. Chelation-enhanced ization of anthracenes to their 9,lO-Dewar isomers. J.Org. Chem.
fluorescence in 9,10-bis(TMEDA)anthracene. J. Am. Chem. SOC. 1989,54, 2336-2341.
1988,110,4460-4462. (151) Chung, J.; Rosenfeld, S.M. 2,7-Dithia[8]-, 2,&dithia[91-, and 2,9-
(129) Fages, F.; Desvergne, J.-P.; Bouas-Laurent, H. Non-linear triple dithia[lO] (9,lO)anthracenophanes. High reactivity induced byaryl-
exciplexes: thermodynamic and kinetic aspects of the intramo- ring deformation. J. Org. Chem. 1983, 48, 387-388.
lecular exciples formation between anthracene and two anchored (152) Rosenfeld, S. M.; Shedlow, A. M.; Kirwin, J. M.; Amaral, C. A.
nitrogens of an anthraceno-cryptand. J. Am. Chem. SOC.1989, Structure and reactivity in 9,lbbridged anthracenes. J.Org. Chem.
111,96-102. 1990,55, 1356-1359.
(130) Fages, F.; Desvergne, J.-P.; Bouas-Laurent, H.; Marsau, P.; Lehn, (153) Schoof, S.;Gbten, H. Radiationless deactivation of the fluorescent
J.-M.; Kotzyba-Hibert, F.; Albrecht-Gary, A.-M.; Al-Joubbeh, M. state of 9-methoxyanthracene and of related meso-substituted
Anthraceno-Cryptands: A new class of cation-complexing mac- anthracenes. Ber. Bunsen-Ges. Phys. Chem. 1989, 93, 864-870.
robicyclic fluorophores. J. Am. Chem. SOC.1989,111,8672-8680. (154) Gbten, H.; Mintaa, M.; Klasinc, L. Deactivation of the fluorescent
131) Huston, M. E.; Akkaya, E. U.; Czarnik, A. W. Chelation enhanced state of 9-tert-butylanthracene. 9-tert-Butyl-Dewar anthracene.
fluorescence detection of non-metal ions. J. Am. Chem. SOC.1989, J. Am. Chem. SOC.1980,102, 7936-7937.
111,8735-8737. (155) Dreeskamp, H.; Jahn, B.; Pabst, J. Thermoreversiblephoto valence
132) Fages, F.; Desvergne, J.-P.; Bouas-Laurent, H.; Lehn, J.-M.; isomerization of 9-t-butylanthracene to ita 9,lO-Dewar-isomer. Z .
Konopelski, J. P.; Marsau, P.; Barrans, Y. Synthesis and fluores- Naturjorsch. 1981,36a, 665-668.
cence emission properties of a bis-anthracenyl macrotricyclicditopic (156) Jahn, B.; Dreeskamp, H. 2.Naturforsch. 1982,37a, 376-379.
receptor. Crystal structure of its dinuclear Rubidium cryptate. J. (157) Jahn, B. Dissertation,Technische Universiut Braunschweig, 1983.
Chem. Soc., Chem. Commun.1990,655-658. (158) Jahn, B.; Dreeskamp, H. Ber. Bunsen-Ges. Phys. Chem. 1984,88,
133) Hinschberger, J.; Desvergne, J.-P.; Bouas-Laurent, H.; Marsau, P. 42-47.
Synthesis and photophysical properties of fluorescent anthra- (159) Kraljic, I.; Mintaa, M.; Klasinc, L.; Ranogajec, F.; Gbten, H.
cenophanes incorporating two polyoxadioxoalkanechains.J.Chem. Thermo- and photochemical aspects of the valence isomerization
SOC.,Perkin Trans. 2 1990,993-1000. of 9-tert-butylanthracene. Nouu. J. Chim. 1983, 7 , 239-243.
le0 Chemical Reviews, 1993, Vol. 93,No. 1 Bedter

(160) Angermund, K.; Claus, K. H.; Goddard, R.; Krtiger, C. High- (187) Hamanoue, K.;Hirayama, S.; Nakayama, T.; Teranishi, H. Non-
resolution X-ray crystallography-An experimental method for the radiative relaxation process of the higher excited statas of mem-
descriptionofchemical bonds. Angew. Chem.,lnt.Ed.Engl. 1985, substituted anthracenes. J. Phys. Chem. 1980,84, 2074-2078.
24,237-247. (188) Ohtani, H.; Kobayashi, T.; Suzuki, K.; Nagakura, S. Picosecond
(161) Hirayama, S.; Shimono, Y. Temperature and viscosity effects on spectroecopy studies of the intersystem crowing of aromatic
fluorescence in St-butylanthracene, J . Chem. SOC.,Faraday 2 carbonyl and nitro compounds in solution. Bull. Chem. SOC. Jpn.
1984,80, 941-955. 1980,53,43-47.
(162) Meng, J.; Yao, X.;Wing, H.; Matsuura, T.; Ito, Y. Novel photo- (189) Snyder, R.; Testa, A. C. Nature of the low-temperature emieaion
isomerization of 9-tert-butyl-10-cyanoanthraceneinvolving 1,2- from 9-nitroanthracene. J. Phys. Chem. 1981,85, 1871-1873.
transfer of methyl group. Tetrahedron, 1988,44,355-358. (190) Hirayama, S.; Kajiwara, Y.; Nakayama, T.; Hamanoue, K.; Ter-
163) Hirayama, S.; Inoue, T.; Ito, Y.; Matauura, T. Multi-exponential anishi, H. Correct assignment of the low-temperature lumintwcence
analysisof the fluorescencedecaysof 9-cyano-10.t-butylanthracene from 9-nitroanthracene. J. Phya. Chem. 1985,89, 1945-1947,
in PMMA. Chem. Phys. Lett. 1985,115, 79-83. (191) Hamanoue, K.; Amano, M.; Kimoto, M.; Kajiwara, Y.; Nakayama,
164) Mintas, M.; Giisten, H.; Williard, P. G. Synthesis and [4+41 T.; Teranishi, H. Photochemical reactions of nitroautbracene
photodimerization of 9-trifluoromethylanthracene. J . Photochem. derivatives in fluid solution. J . Phys. Chem. 1984,106,5993-5997.
Photobiol. A: Chem. 1989,48,341-345. (192) Testa,A. Luminescence and photochemistry of 9-nitroanthracene
165) Castellan, A.; Desvergne, J.-P.; Bow-Laurent, H. Study of non- a t 4.2 K. J . Photochem. Photobiol. A: Chem. 1989,47,309-318.
conjugated bichromophoric systems called 'jaw photochromic (193) Smith, I.; Testa, A. C. Flash photolysis of molecules implicated in
materials'. 11. Photocyclomerization and fluorescence of bisan- 9-nitroanthracene photochemistry. J . Photochem. Photobiol. A:
thracenes leading to unsymmetrical photodimerization of the Chem. 1989,47, 167-172.
anthracene ring. Nouu.J . Chim. 1979,3, 231-237. (194) Testa, A. C.; Wild, U. P. Holographic photochemical study of
166) Inoue, T.; Kaneda, T.; Mieumi, S. Layered compounds. XXIII. 9-nitroanthracene. J . Phys. Chem. 1986, 90,4302-4305.
Novel photochemical multicycloaddition of anthracenophadiyne. (195) Bradshaw, A. W.; Chapman, 0. L. Photochemistry of sodium
Tetrahedron Lett. 1974,2969-2972. 9-anthroate in aqueous solution. J . Am.Chem. Soc. 1967,89,2372-
2375.
167) Hayashi, T.; Mataga, N.; Inoue, T.; Kaneda, T.; Irie, M.; Misumi, (196) Desvergne, J.-P.; Bouas-Laurent, H.; Castellan, A.; Kowaleki, J.;
S. Photochemical reaction between intramolecular separated Yurek, E.; de Haut de Sigy, A. Fluorescence quenching and
*-electronic systems-photochemistryof [101(9,lO)anthracenopha- photoprotodesilylation of 9-trimethyleilylanthracene in methanol.
4,d-diyne. J. Am. Chem. SOC. 1977,99, 523-526. J. Chem. SOC.,Chem. Commun. 1986, 82-84.
168) Tobe, Y.; Takahashi, T.; Ishikawa, T.; Yoshimura, M.; Suwa, M.; (197) Le FBvre, R. J. W.; Rodom, L.; Ritchie, G. L. D. Molecular
Kobiro, K.; Kakiuchi, K.; Gleiter, R. Bent acenes: Synthesis and polarisability. The conformations of some 9-substituted an-
molecular structure of [6](1,4)naphthalenophane and 161(1,4)- thracenes as solutes. J. Chem. SOC. B 1968,775-778.
anthracenophane. J . Am. Chem. SOC. 1990,112, 8889-8894. (198) Andereeon,K.;Becker,H.-D.;Engelhardt,L.M.;Haneen,L.;White,
(169) Tobe, Y.; TaLahaehi, T.; Kobiro, K.; Kakiuchi, K. Photochemical A. H. Molecular geometry and crystal structure of 9-acetylan-
[2+2] dimerization of [61(1,4)-anthracenophane. J. Am. Chem. thracene. A u t . J . Chem. 1984, 37,1337-1340.
SOC. 1991,113,5804-5808. (199) Swayambunathan, V.; Lim, E. C. Torsionaldynamics of 9-carbonyl
(170) Kammula, S. L.; Iroff, L. D.; Jones, M., Jr.; van Straten, J. W.; de substituted anthracenes. J . Phys. Chem. 1986,89,396&3962.
Wolf, W. H.; Bickelhaupt, F. Interconversion of [6lparacycIophane (200) Hirayama, S.; Kobayashi, T. Picosecond-laser study of triplet
and 1,4-hexa~nethylene(Dewar benzene). J . Am.Chem. SOC. 1977, population of carbonyl derivatives of anthracene. Chem. Phys.
99,5815. Lett. 1977, 52, 55-58.
(171) Tobe, Y.; Takahaehi, T.; Kobiro, K.; Knkiuchi, K. Thermalvalence (201) Matsumoto,T.;Sato, M.;Hirayama,S. Newphotochemicalreactiona
isomerization of hemi-Dewar type isomers of [61(1,4)naphthaleno of 9-w-bromoacetylanthracene. I. Bull. Chem. SOC.Jpn. 1974,47,
and [61(1,4)anthracenophanes. Chem. Lett. 1990, 1587-1590. 358-363.
(172) Tobe, Y.; Jimbo, M.; Kobiro, K.; Kakiuchi, K. Telomers of bent (202) Mataumoto,T.; Sato, M.; Hirayama, S. Photolysisof a-haloketones.
arenes. Acid-catalyzed dimerization and trimerization of the 1,4- 11. Intramolecular reactions of 9-a-bromopropionylanthracene.
hesamethylene-bridged arenes [6lparacyclophane, [6](1,4)-naph- Bull. Chem. SOC.Jpn. 1975,48, 1659-1660.
thalenophane, and [61(1,4)anthracenophane. J . Org. Chem. 1991, (203) Matsumoto, T.; Sato, M.; Hirayama, S. Efficient intersystem
56,5241-5243. crowing mechanism revealed by a large temperature effect on the
(173) Tobe, Y.; Takemura, A.; Jimbo, M.; Takahaahi, T.; Kobiro, K.; photochemicalreactions of 9-a-bromopropionylanthracene. Chem.
Kakiuchi, K. Unusual reactivity of bent acenes: Reactions of 161- Phys. Lett. 1974,27,237-240.
(1,4)naphthalenophane and [6] (1,l)anthracenophane with elec- (204) Palm, W.-U. Dissertation, Technische Universitit Braunschweig,
trophiles. J . Am. Chem. SOC. 1992, 114, 3479-3491. 1990.
(174) (a) Miki, S.; Shimizu, R.; Nakatsuji, H. Synthesis and properties (205) Palm, W. U.; Dreeskamp, H.; Bow-Laurent, H.; Castellan, A. The
of [6](1,4)cyclophaneanthraquinone: A novel anthraquinone de- photochemistry of a-phenoxyacetophenones investigated by flash-
rivative undergoing photovalenceisomerization. Tetrahedron Lett. CIDNP-spectroscopy. Ber. Bunsen-Cea. Phys. Chem. 1992, 96,
1992,33,953-956. (b) Miki, S.; Matsuo, K.; Yoshida, M.; Yoshida, 50-81.
2. Novel anthraquinone derivatives undergoing photochemical (206) Becker, H.-D.; Skelton, B. W.; White, A. H. Photochemical
valence isomerization. Tetrahedron Lett. 1988,29,2211-2214. isomerization of (E,2)-1,5-bis(9-anthryl)penta-l,rl-dien-&one and
(175) Nakayama, T.; Yamaguchi, T.; Ushida, K.; Hamanoue, K.; Miki, ita intramolecular Diels-Alder adduct. Awt. J . Chem. 1986,38,
S.; Matauo, K.; Yoshida, 2.Phosphorescence and triplet-triplet 1471-1480.
absorption spectra of 1,2,3-tri-t-butylanthraquinone and 1,2-di-t- (207) Becker, H.-D.; Andersson, K.; Sandros, K. Photochemistry of the
butyl-3-trimethylailylanthraquinone. Chem.Phys. Lett. 1988,148, anthracene chromophore: The dimerization of trane-l-(Q-anthryl)-
259-263. 2-phenylethylene. J. Org. Chem. 1985,50, 3913-3916.
(176) Sigman, M. E.; Zingg, S. P.; Pagni, R. M.; Burns, J. H. Photo- (208) Rigaudy, J.; Igier, C.; Barcelo, J. Directing effect of bases on the
chemistry of anthracene in water. Tetrahedron Lett. 1991, 32, photoreactions of polycyclicaromatic azides. Syntheaieof 'ortho"-
5737-5740. fused azepines in the anthracene and naphthalene aeries. Tet-
(177) Mber, G. 2.Wiss.Photogr. Photophys. Photochem. 1965,59,20- rahedron Lett. 1975, 3845-3848.
32. (209) Astles, D. J.; Girard, M.; Griller, D.; Kolt, R. J.; Wayner, D. D. M.
(178) Uber, G. 2.Phys. Chem. N.F. 1967,54,73-76. The unusual reactivity of 9,9'-dianthrylcarbene. J . Org. Chem.
(179) Kanyura? N.; Nagakura, S. Photoinduced anthrone to anthranol 1988,53,6053-6057.
isomerization in ethyl ether. J. Am. Chem. SOC. 1968, 90, 6905- (210) Becker, H.-D.; Becker, H.-C.; Sandros, K.; Andereeon, K. Photo-
6909. chemistry of the anthracene chromophore: Novel isomerization of
1-(9-anthry1)-2-benzoylethylenes.Tetrahedron Lett. 1985, 26,
(180) Mauser, H.; Gauglitz, G . Chem. Ber. 1973,106, 1985-1992. 1589-1592.
(181) Mills, S. G.; Beak, P. Solvent effects on keto-enol equilibria: Testa (211) Lower, S. K.; El-Sayed, M. A. The triplet state and molecular
of quantitative models. J . Or#. Chem. 1985,50,1216-1224. electronic processes in organic molecules. Chem. Reu. 1966, 66,
(182) Netto-Ferreira, J. C.; Murphy, W. F.; Redmond, R. W.; Scaiano, 199-241.
J. C. Photochemistry and photophysics of ketyl radicals containing (212) b o l a , A. A., Turro, N. J., Eda. Energy transfer and organic
the anthrone moiety. J. Am. Chem. Soc. 1990, 112, 4472-4476. photochemistry. Technique of organic chemistry;Leermnkers, P.
(183) Scnino, J. C.; Lee, C. W. B.; Chow, Y. L.;Buono-Core, G. E. Laser A., Weissberger,A,, Eds.;Interscience Publishers: New York, 1969;
flash studies of the photochemistry of anthrone. J. Photochem. VOl. XIV.
1982,20,327-334. (213) Turro, N. J.; h a m u r t h y , V.; Cherry, W.; Fameth, W. The effect
(184) Manring, L. E.; Peters, K. S. Picosecond Dynamics of Proton of wavelength on organic photoreactions in solution. Reactions
Transfer. J . Am. Chem. SOC. 1985,107,6452-6458. from upper excited states. Chem. Rev. 1978, 78,125-145.
(185) Chapman, 0. L.; Heckert, D. C.; Reasoner, J. W.; Thackaberry, S. (214) Speiaer, S. Novel aspects of intermolecular and intramolecular
P. Photochemicalstudies on 9-nitroanthracene. J . Am.Chem. SOC. electronic energy transfer in solution. J . Photochem. 1983, 22,
1966,88,5550-5554. 195-2 11.
(186) Chapman, 0. L.; Lee, K. The structures of the photodimers of (215) Haeeoon, 5.; Lustig, H.; Rubin, M.; Speiaer, S. The mechanism of
9-nitroanthracene, 9-aminoanthracene, and 9-anthrylisocyanate. short-range intramolecular electronic energy transfer in bichro-
J . Org. Chem. 1969,34, 4166-4168. mophoric molecules. J . Phys. Chem. 1984,88,6367-6374.
Unimolecular Photochemistry of Anthracenes Chemical Reviews, 1993, Voi. 93, No. 1 160

(216) Speiser, S.; Hassoon, S.; Rubin, M. The mechanism of short-range (240) Saeva, F. D.; Breslin, D. T. Intramolecular photochemical rear-
intramolecular electronic energy transfer in bichromophoric mol- rangement via an in-cage cation-radicalhadical pair of an anthr-
ecules. 2. Triplet-triplet transfer. J. Phys. Chem. 1986,90,5085- ylsulfonium salt derivative. J. Org. Chem. 1989,54, 712-714.
5089. (241) Saeva, F. D.; Breslin, D. T.; Luse, H. R. Intramolecular photo-
(217) Wou, J. S.; Valdes-Aguilera, 0.; Neckers, D. C. Synthesis and induced rearrangements via electron-transfer-induced, concerted
spectral propertieaof Rose Bengalderivativeacontaininganthracene bond cleavage and cation radicaltradical coupling. J. Am. Chem.
chromophores. J.Photochem. Photobiol., A: Chem. 1989,46,87- SOC.1991,113,5333-5337.
97. (242) &ton, D. F. Electron transfer induced photofragmentation as a
(218) Zhou,Q.;Shen,S.;Yuan, Z.;Shen,T.Effectofexcitationwavelength route to free radicale. Pure Appl. Chem. 1984,56, 1191-1202.
on the photophysics of fluorescein-anthracenemethyl ester. J. (243) He, X.; Huang, W.-Y.; Reiser, A. Wavelength dependence of the
Photochem. Photobiol., A: Chem. 1990,51, 229-235. photolysis of some anthracene-containing sulfonium salts. J. Org.
(219) Arden, J.; Deltau, G.;Huth, V.; Kringel, U.; Peros, D.; Drexhage, Chem. 1992,57, 759-761.
K. H. Fluorescence and lasing properties of rhodamine dyes. J. (244) Yamaoka,T.; Adachi,H.; Matsumoto, K.; Watanabe, H.; Shiromki,
Lumin. 1991,48 and 49,352-358. T. Photochemical dissociation of gnitrobenzyl 9,lO-dimethoxy.
(220) Effenberger, F.; GBtz, G.; Bluerle, P. Chem. Ber. 1992,125,941- anthracene-2-sulphonate via intramolecular electron transfer. J.
950. Chem. SOC.,Perkin Tram. 2 1990, 17W1714.
(221) Effenberger,F.; Schlosser,H.;Biuerle,P.;Maier,S.;Port, H.; Wolf, (245) Naitoh, K.; Yoneyama, K.; Yamaoka, T. Photoinduced intramc-
H. C. Synthesis and optical properties of terminally substituted lecularelectron transfer mechanism for photochemicaldiseociation
conjugated polyenes. Angew. Chem.,Znt. Ed. Engl. 1988,27,281- of para-substituted benzyl 9,10-dimethoxyanthracene-2-sdfonatea.
284. J. Phys. Chem. 1992, W,238-244.
(222) Mau, A. W. H.; Sasse, W. H. F.; Creaser, I. I.; Sargeson, A. M. (246) Arai, T.; Karatsu, T.; Sakuragi, H.; Tokumaru, K. 'One-way"
Photoproduction of hydrogen from linked chromophores: An- photoisomerizationbetween cis- and trans-olefin. A novel adiabatic
thracene and cobalt cage complex. Nouu. J. Chim. 1986,10,589- process in the excited state. Tetrahedron Lett. 1983,24, 2873-
592. 2876.
(223) Creaser, I. I.; Hammershoi, A.; Launikonis, A.; Mau, A. W.-H.; (247) Tokumaru, K.; Arai, T. Potential energy surfaces of one-way and
Sargeson, A. M.; Sasse, W. H. F. Photoproduction of hydrogen twc-way photoisomerization of olefins. J.Photochem. Photobiol.
from linked chromophores: Anthracene and cobalt cnge complexes A: Chem. 1992,65, 1-13.
- 11. Photochem. Photobiol. 1989,49, 19-23. (248) Arai, T.; Karatsu, T.; Sakuragi,H.; Tokumaru, K.; Tamai, N.;
(224) Boyde, S.; Strouse, G. F.; Jones, W. E.; Meyer, T. J. Intramolecular Yamazaki, I. Effects of ,9-substituents on internal rotation of the
energytransfer in a chromophore-quenchercomplex. J.Am. Chem. anthryl group of 2-anthrylethylenes in the excited state. J.
SOC.1989, 111,7448-7454. Photochem. Photobiol. A: Chem. 1992,65, 41-51.
(225) MacQueen,D. B.; Eyler, J. R.; Schanze,K. S. Intramolecular energy (249) Becker, H.-D.: Sbrensen, H.; Sandros, K. Photochemical isomer-
transfer in the inverted region. J.Am. Chem. Soc. 1992,114,1897- ization and dimerization of 1-(9-anthryI)-2-nitroethylene.J. Org.
1898. Chem. 1986,51,3223-3226.
(250) Becker, H.-D.; Skelton, B. W.; Stirensen, H.; White, A. H.
(226) Becker,H.-D.;Sandros,K.;Skelton,B. W.;White,A.H.Relationehip Photochemical cis-trans isomerization of 2-substituted B(2-nitrc-
between fluorescence and molecular geometry. Excimer lumines- etheny1)anthracenes. X-ray structure analyses of (E)- and (2)-9-
cence of crystalline spiroanthronyl-substituted dihydrobenzan- (2-nitro-2-phenyletheny1)anthracene. A u t .J. Chem. 1989,42,593-
thracenes. J. Phys. Chem. 1981,85,2923-2926. 601.
(227) Becker,H.-D.;Sandros, K.;Skelton,B. W.;White,A.H. Relationehip (251) Sandros,K.; Becker, H.-D. Adiabatic Photochemical isomerization
between fluorescence and molecular geometry. Proximity effects of cis-l-(9-anthryl)-2-phenylethylenes.J. Photochem. 1987, 39,
in fluorescence quenching by anthrone-anthracene interaction. J. 301-315.
Phys. Chem. 1981,85, 2927-2930. (252) Giirner, H. J. cis-trans Photoisomerization of 1-(9-anthryl)-2-
(228) Zimmerman, H. E.; Amick, D. R. Photochemistry of Anthrabar- phenylethylenes: Effects of substitution and solvent polarity. J.
relene. J. Am. Chem. SOC.1973,95,399-3982. Photochem. Photobiol. A: Chem. 1988,43,263-289.
(229) Okada, K.; Sakai, H.; Oda, M.; Yoshimura,A.; Ohno, T. Asymmetric (253) Sandros, K.; Becker, H.-D. Comments on 'cis-tram Photoisomer-
induction via intramolecular Trsensitization: Photoisomerization ization of l-(g-anthryl)-2-phenylethylenes: Effecta of substitution
of a-(Y'-anthryl)ethyl spiro[cyclopropane-l,9'-fluorene]-2-~arbox- and solvent polarity". J. Photochem. Photobiol. A: Chem. 1988,
ylates. Tetrahedron Lett. 1989,30, 1091-1094. 43,291-292.
(230) Okada, K.; Samizo, F.; Oda, M. Photochemical reactions of (9- (254) Bartocci, G.;Masetti, F.; Mazzucato, U.; Spalletti, A.; Orlandi, G.;
anthry1)methyl methyl fumarate and maleate: Application to Poggi, G. A photophysical and theoretical study of styrylan-
asymmetric [4+2]-phot~cycloaddition reaction. TetrahedronLett. thracenes. J. Chem. SOC.,Faraday Trans. 2, 1988,385-399.
1987,33, 3819-3822. (255) Orlandi, G.; Negri, F.; Mazzucato, U.; Bartocci, G.TI potential
(231) Liu, R. S. H.; Edman, J. R. The role of second triplet states in energy curvea and "one-way" photoisomerizationof styrylaromatica.
solution photochemistry. I. Reactions of rigid systems sensitized J. Photochem. Photobiol. A Chem. 1990,55,37-42.
by anthracene and substituted anthracenes. J. Am. Chem. SOC. (256) Grner, H.; Elisei, F.; Aloisi, G. G. Photoinduced electron transfer
1968, 213-215. between styrylanthracenes and electron donors and acceptors in
(232) Liu, R. S.H.; Edman, J. R. Triplet-triplet energy transfer from the acetonitrile. J. Chem. SOC.,Faraday Trans. 1992,88, 29-34.
second triplet states of anthracenes. Chemical studies. J. Am. (257) Aseleson, 0. Synthesis and photochemical E-2-isomerization of
Chem. SOC.1969,91,1492-1497. substituted 9-styryhthracenes and some related anthrylethylenea.
(233) Kavarnos, G. J.; Turro, N. J. Photosensitization by reversible Thesis, Gothenburg U., 1989.
electron transfer: theories, experimental evidence, and examples. (258) Becker, H.-D.; Hansen, L.: Andersson, K. cis-1,2-Di(9-anthr~l)-
Chem. Rev. 1986,86,401-449. ethylene. J. Org. Chem. 1981,46, 5419-5422.
(234) Fox, M. A., Chanon, M., Eds.Photoinduced Electron Transfer; (259) Becker, H.-D.; Sandros, K.; Andersson, K. cis-1,2-Di-(9-anthryl)-
Eleevier: Amsterdam, 1988. ethylene: Photochemical isomerization by intramolecular Diels-
(235) Gust, D., Moore,T. A., Ed. Covalentlylinked donor-acceptorspecies Alder addition. Angew. Chem., Znt. Ed. Engl. 1983,22,495-496;
for mimicry of photosynthetic electron and energy transfer. Angew. Chem., Suppl. 1983,609-619.
Tetrahedron Symposia-in-Print Number 39. Tetrahedron 1989, (260) Becker, H.-D.; Skelton, B. W.; White, A. H. Molecular geometry
45,4669-4911. of 1,2-bie(g-anthryl)acetylene. Aust. J.Chem. 1985,38,1567-1670.
(236) Mattay, J. Ed. Photoinduced ElectronTransfer. Top. Curr. Chem. (261) Gtirner, H.; Fischer, E.; Castel, N. Photophysica and reversible
1990,156; 1990,158; 1991,159. photochemistryof9-anthrylazomethines.J.Photochm. Photobiol.
(237) (a) Electron Transfer. Fox, M. A., Ed. Chem. Reu. 1992,92,365- A: Chem. 1990,52, 123-136.
490. See: Wasielewski, M. R. Photoinduced electron transfer in (262) Furuuchi. H.; Arai. T.; Sakureni, H.; Tokumaru. K.; Nishimura, Y .:
supramolecular systems for artificial photosynthesis. Chem. Rev. ~ a m a ~ a l I.
r iNovei
, rotational ikmerization of inthracene nucieui
1992, 92, 435-461. around its bond connecting to C=N bond in the excited singlet
(238) (a) Larson, J. R.; Petrich, J. W.; Yang, N. C. Intramolecular state of (E)-N-methoxy-l-(2-anthryl)ethanimine. J. Phys. Chem.
exciplexea of polychromophoricmolecules. J.Am. Chem.SOC.1982, 1991,95,10322-10325.
104,5000-5002. (b) Yang, N.-C.; Gerald, R., 11; Wasielewski, M. (263) Paetzold, R.; Reichenblcher, M.; Appenroth, K. 2.Chem. 1981,21,
R. Chemistry of exciplexes. 19. Exciplex-promoted electron 421-430.
transfer in l-(phenylamino)-3-(9-anthryl)propanes.J.Am. Chem. (264) Appenroth, K.; Reichenbicher, M.; Paetzold, R. Thermochromism
SOC.1985,107,5531-5532. (c)Yang,N.C.;Mimk,D. W.; Johnson, and p h o t o c h r o " of aryl-substituted acyclic &ea. V Quench-
D. G.; Larson, J. R.; Petrich, J. W.; Gerald, R., 111; Wasielewski, ing of the photochemical E - 2 isomerization via FBrster energy
M. R. Photochemistry of polychromophoric arylamines. Tetra- transfer. J. Photochem. 1983,22, 263-273.
hedron, 1989,45,4669-4681. (d) Heitele, H.; Finck, P.; Weeren, (265) Appenroth, K.; Birckner, E.; Reichenbicher, M. 2.Chem. 1986,26,
S.; Pbllinger, F.; Michel-Beyerle, M. E. Solvent polarity effects on 106-107.
intramolecular electron transfer. 1. Energetic aspects. J. Phys. (266) Appenroth, K.; Birckner, E.; Reichenblcher, M. Thermochromism
Chem. 1989,93,5173-5179. and photochromism of aryl-substituted acyclic azines. X. Rea-
(239) Sugimqto, A.; Yamano, J.; Yoneda, S. Photochemical behaviour of lationship between moleculargeometryand fluorescenceof anthryl-
9-(2-anilinoethyl)- and 9-(3-anilinopropyl)anthracenesin various substituted compounds. J. Photochem. 1987,37, 117-124.
solvents. J. Chem. SOC.,Perkin Tram. 1 1989,483-487. (267) Brockmann, H.; M W a n n , R. Chem. Ber. 1949,82,348-357.
170 Chemical Reviews, 1993, Vd. 93,No. 1

(268) Korenstein, R.; Muszkat, K. A.; Fischer, E. The irreversible (297) Iwama,A.;Toyoda,T.;Yoshida,M.;Oteubo,T.;Sakata,Y.;Misumi,
photochemistry of bianthrone. Helu. Chim. Acta 1976,59,1826- S. Layered compounds. LII. Syntheses of eleven anthra-
1831. cenophanes. Bull. Chem. SOC. Jpn. 1978,51,2988-2994.
(269) Scholz,M.; Dietz,F.; MiihlstAdt, M. TetrahedronLett. 1970,2835- (298) Sauer, M.; Staab, H. A. Liebigs Ann. Chem. 1984,615-617.
2838. (299) h v e r g n e , J.-P.; Bow-Laurent, H. Cation complexing photo-
(270) Madding, D. R. A photochemical preparation of 4,ll-diphenyl- chromic materials involving bisanthracenes linked by a polyether
bieanthene. J . Org. Chem. 1970,35, 1221-1223. chain. Preparation of a crown-ether by photocyclomerization. J .
(271) Filipescu, N.; Avram, E.; Welk, K. D. Photooxidative traneforma- Chem. SOC.,Chem. Commun. 1978,403-404.
tions of anthrone, bianthronyl, and bianthrone in acid solution. J . (300) Deavergne, J.-P.; Bouas-Laurent, H. Study of nonconjugated
Org. Chem. 1977,42,507-512. bichromophores linked by a polyether chain. I. Photochemical
(272) Laarhoven, W. H.; Cuppen, Th. J. H. M.; Nivard, R. J. F. synthesis of crown ethers from bis-(g-anthrylory) polyoxaalkanes.
Photocyclizationsin stilbene-like compounds. -111. Effect of steric Isr. J . Chem. 1979,18, 220-226.
factors. Tetrhaedron, 1970,4865-4881. (301) Yamashita, I.; Fujii, M.; Kaneda, T.; Misumi, S.;Oteubo, T.
(273) Laarhoven, W. H. Aspects of the photochemistry of aryl ethylenes. Synthetic macrocyclic ligands. 11. Synthesis of a photochromic
Pure Appl. Chem. 1984,56, 1225-1240. crown ether. Tetrahedron Lett. 1980,21,541-544.
(274) Segura, C.; Parella, T.; Sanchez-Ferrando, F.; Bouae-Laurent, H.; (302) Bouas-Laurent, H.; Castellan,A.; Desvergne,J.-P. From anthracene
Desvergne, J.-P. Stilbene to phenanthrene type photocyclization photodimerizationtojaw photochromicmaterials and photorowns.
of a bis(4-anthry1)ethylene. A new access to the dibenzopicene Acre Appl. Chem. 1980,52, 2633-2648.
skeleton. Bull. SOC. Chim. Belg. 1992, 101, 513-517. (303) Deavergne, J.-P.;Castellan, A.; Lesclaux,R. Study of non-conjugated
(275) Hayward, R. J.; Leznoff, C. C. Photocyclization reactions of aryl bichromophores linked by a polyether chain. Kinetic analysis of
polyenes 11. The Photocyclization of l-aryl-dphenyl-1,3-buta- the formation of intramolecularexcimersand photocyclomerization
dienes. Tetrahedron 1971,27, 2085-2090. of some bhthracenes. Chem. Phvs. Lett. 1980. 71.228-231.
(276) Broene, R. D.; Diederich, F. The synthesis of circumanthracene. (304) Desvergne, J.-P.; Bitit, N.; Bouas&urent, H. J . h e m . Res. (M)
Tetrahedron Lett. 1991,32,5227-5230. ----.
lW4. 1901-1921.
~ - ~-~~
- ~
(305) Desvergne,J.-P.;Bitit, N.; Castellan, A.; Webb, M.; Bows-Laurent,
(277) Couture, A.; Lablache-Combier, A.; Lapouyade, R.; Felix, G.
Photochemical and thermal reactions of 9-anthrylmethyl sulphide H. Non-conjugated bichromophoric Systems. Part 4. Synthesis
and selenides. New synthesis of lepidopterene. J. Chem. Res. (8) and photochemical study of bis-9-anthryl with a four-membered
1979, 258-259; J . Chem. Res. (M) 1979, 2887-2897. chain; influence of the replacement of methylene links by oxygen
(278) Vermeersch, G.; Febvay-Garot, N.; Caplain, S.; Couture, A.; a t o m or dimethylailyl groups on the formation of intramolecular
Lablache-Combier, A. Tetrahedron Lett. 1979, 609-612. excimem and photocyclomers. J. Chem. SOC.,Perkin Trans. 2,
(279) Holdcroft, S.;Yuen, K. H.; Guillet, J. E. Studies of the photolysis 1988,1885-1894.
of aromatic esters in solution and in polymeric films. J. Polym. (306) Becker, H.-D.; Hammarberg, E.; Skelton, B. W.; White, A. H.
Sci., A: Polym. Chem. 1990,28,1495-1505. Formation and photochemical rearrangement of carbon-oxygen
(280) Holdcroft, S.; Tang, B.-Z.; Guillet, J. E. Two-photon chemistry: linked anthracenes. Tetrahedron Lett. 1989,30, 2137-2140.
Facile synthesis of naphthalene- and anthracene-labelled poly- (307) Becker, H.-D.; Hansen, L.; Andernson, K. Synthesis and photo-
styrene by photolysis of aromatic eaters. J . Chem. Soc., Chem. chemical isomerization of 1,2-di-9-anthrylethanol and 1,2-di-9-
Commun. 1991, 280-282. anthrylethanone. J. Org. Chem. 1986,51, 2956-2961.
(281) (a) Applequiet, D. E.; Lintner, M. A.; Searle, R. Photocyclization (308) Becker, H.-D.; Langer, V.; Skelton, B. W.; White,A. H. Molecular
of compounds containing two anthracene rings. J. Org. Chem. structureeofdi(9-anthryl)methanolanddi(9anthryl) ketone. A u t .
1968, 33, 254-259. (b) Applequist, D. E.; Swart, D. J. 9,W- J. Chem. 1989,42,603-610.
Dianthrylmethane derivatives. Conjugate rearrangements and (309) Becker, H.-D.; Skelton, B. W.; White, A. H. Molecular topology of
photocyclizations. J . Org. Chem. 1975,40, 1800-1804. linked anthracenes: X-ray structure analyses of alkyl di-9-anthryl-
(282) Bergmark, W. R.; Jones, G., II; Reinhardt, T. E.; Halpem, A. M. glycolate, 9-anthryl B-anthrylmethyl ethers, and their photoiso-
Photoisomerization of bis(9-anthrybethane and other linked an- men. A u t . J. Chem. 1989,42, 1869-1880.
thracenes. The role of excimersand biradicalsin photodimerization. (310) Livingaton, R.;Wei, K. S.Reversible photoisomerization of 1,2-
J . Am. Chem. SOC. 1978,100,66654673, bis(9-anthry1)ethane. J. Am. Chem. SOC. 1967,89,3098-3100.
(283) Ferguson, J. Absorption spectro~copyof sandwich dimers and (311) Castellan, A.; Desvergne, J.-P.; Bouas-Laurent, H. Kinetic study
cyclophanes. Chem. Reu. 1986,86,957-982. of photophysical and photochemical procesees in a,o-(bis-9-
(284) Golden, J. H. Bi(anthracene-9,lO-dimethylene)(tetrabenz0[2,21- anthrylbalknuea (ethaneto decane) at room temperature. Chem.
paracyclophane). J . Chem. SOC. 1961, 3741. Phys. Lett. 1980, 76,390-396.
(285) Hayashi, T.; Mataga, N.;Sakata,Y.; Misumi, 5.;Morita, M.;Tanaka, (312) Bergmark, W. R.; Jones, G., 11. Photoisomerization of linked
J. Excimer flwrcscence and photodimerimtionof anthracenophanea anthracenes. A. demanding test of molecular geometry for
and 1,2-dianthrylethanes. J . Am. Chem. SOC. 1976,98,5910-5913. intermediates in photodimerization. Nouv. J . Chim. 1977,1,271-
(286) Morita,M.;Kishi,T.;Tanaka,M.;Tanaka,J.;Ferguson,J.;Sakata, 273.
Y.: Misumi. S.: Havashi. T.: Mataea. N. Electronic abeomtion and (313) (a) Fergueon, J. Mechanism of photocycloaddition in a,o-(bis-9-
fluorescence s&&a of [2.2lanthr>cenophanes. Bull. Chem. SOC. anthry1)-n-alkanes. Chem.Phys.Lett. 1980,76,398-402. (b)Jones,
Jpn. 1978,51,3449-3457. G., 11.; Bergmark, W. R.; Halpem, A. M. Comment on Mechanism
(287) Mau, A. W. H. Solid state reversible reactions. Thermal behaviour of photocycloaddition in a,w-(bis-9-anthryl)-n-alkanes.Chem.
of the photoisomer of bi[anthracene-9,10-dimethylenel.J . Chem. Phys.Lett. 1980, 76,403-405.
SOC.,Faraday Trans. 1978,1,603-612. (314) Becker, H.-D.; Elebring, T.; Sandroe, K. Photochemical intramo-
(288) Dunand,A.;Ferguson, J.;Puza,M.;Robertaon,G.B.Conformational lecular 4r+4r cycloaddition of 1,2-di(9-anthryl)ethanes,J. Org.
effects in the absorption spectra and photochemistry of [2.n]- Chem. 1982,47, 1064-1068.
(9,10)-anthracenophanes (n = 2,3). Chem. Phys. 1980, 53, 225- (315) Manring, L. E.; Peters, K. S.; Jones, G., 11.; Bergmark, W. R.
234. Observation of a common intermediate in the photocycloaddition
(289) Ehrenberg, M. The crystal structure of bi(anthracene-9,lO-di- andphotocycloreversion of linked anthracenes. J . Am. Chem.SOC.
methylene) photoisomer. Acta Crystallogr. 1966, 20, 183-186. 1986,107, 1485-1489.
(290) Wada, A.; Tanaka, J. The molecular structure of bi(anthracene- (316) (a)Becker, H.-D.; Andemon, K. Photochemietryof theanthracene
9,lO-dimethylene). Acta Cystallogr. 1977,833, 355-360. chromophore: Triplet-sensitized isomerizationof dianthrylethanea.
(291) Toyoda, T.; Misumi, S. Layered compounds. LI. The crystal Tetrahedron Lett. 198S,26,6129-6132. (b) Becker, H.-D.; Ander-
structure of syn42.21anthracenophane. Tetrahedron Lett. 1978, ason, K. Novel polycyclicaromatic hydrocarbons by intramolecular
1479-1482. Diela-Alder reaction: From lepidopterenes to benzenobenzopen-
(292) Dunand,A.;Ferguson, J.;Puza,M.;Robertaon,G.B.Conformational taphenea viadmthrylethanes. Tetrahedron,1986,42,1565-1660.
effects on the fluorescence and photochemistry of [2.nl-(9,10)- (317) Becker, H.-D.; A n d e m n , K. Dienophilicanthracenes: Formation
anthracenophanes (n = 4,5). J. Am. Chem. SOC. 1980,102,3524- of novel triptycenes via thermal and photochemicalintramolecular
3530. Dieb-alder reactions ofdianthrylethanea. TetrahedronLett. 1983,
(293) Shinmyozu, T.; Inazu, T.; Yoshino, Intramolecular cycloaddition 24,3273-3n6.
products of tetraethyl [3.31(1,4)~phthaleno(9,10)an~mnopha (318) (a) Saltiel, J.; Marchand, G. R.; Dabestani, R.; Pecha, J. M. The
2,2,15,15-tetracarboxylateand tetraethyl [3.3lparacyclo(9,10)- quenching of anthracene tripleta by ground-state anthracene.
anthracenophane-2,2,11,11-tetracarboxylate.Chem. Lett. 1978, Chem.Phys.Lett. 1989,100,219-222. (b)Charlton,J.L.;Dabeatani,
405-408. R.; Saltiel, J. Role of triplet-triplet annihilation in anthracene
(294) Tazuke, S.;Watanabe, H. Photoisomerizationand thermalreversion dimerization. J. Am. Chem. SOC. 198a,105,3473-3476.
of [3.31(1,4)naphthaleno(9,lO)anthracenophane derivatives. Tet- (319) Becker, H.-D.; Sbensen, H.; Hammarberg, E. 9,W-Anthril. Tet-
rahedron Lett. 1982,23, 197-200. rahedron Lett. 1989, 30,989-992.
(295) Usui,M.; Nishiwaki, T.; Anda, K.; Hida, M. Cyclophanescontaining (320) Becker, H.-D.; Skelton, B. W.; White,A. H. Molecular topology of
nitrogen atoms in the bridged chains. Photochromism of N,N- di(Banthry1)ethanedione(9,W-anthril)and somegeneridy related
bis(arylsulfonyl)-2,1 l-diaza[3.3l-paracyclo(9,l0)anthra- cyclic 1,2-diketones. A u t . J . Chem. 1991,44, 181-195.
cenophanes. Chem. Lett. 1984,1561-1564. (321) Becker, H.-D.; Kildea, J. D.; Patrick, V. A,; Skelton, B. W.;White,
(296) Ferguson, J.; Puza, M.; Robbins, R. J. Spectrcmopy and photo- A. H. Molecularstructuresand conformationsof 9,9-anthroin, (a
chemistry of a derivative of an anthracene-naphthalene phane. J . and 8 forms), 9,W-anthroin acetate, and some related benzoin
Am. Chem. SOC. 1985, 107, 1869-1874. derivatives. A u t . J . Chem. 1991, 44, 1737-1747.
Unlmolecular Photochemistry of Anthracenes Chemical Revlews, 1993, Vol. 93, No. 1 171

(322) Becker, H.-D.;Amin,K. A. Synthesisand photochemical properties (348) Desvergne, J.-P.; Bitit, N.; Pillot, J.-P.; Bow-Laurent, H. DL-
of 1,3-di-9-anthryl-2-propanol, 1,3-di-9-anthrylacatone,and related symmetrical photodimerization of anthracenes: A new example
propano-linked anthracenes. J. Org. Chem. 1989,54,3182-3188. related to the conformation properties of the silicon hinge linking
(323) Tazuke, S.;Miyamoto, Y.; Ikeda,T.; Tachibana, K. Enantioeelective the two chromophores. J. Chem. Res. (S)1989,146-147.
photoisomerization of 1,3-bis(9-anthryl)propane-l-o1in poly- (349) Ferguson, J.; Castellan, A.; Desvergne, J.-P.; Bow-Laurent, H.
(methyl-L-glutamate) matrix. Chem. Lett. 1986, 953-956. Excimer intermediate in the unsymmetrical photodimerization of
(324) Zachariaese, K. A.; Kiihnle, W. Intramolecular excimers with a,@- the anthracene ring system. Chem. Phys. Lett. 1981,78,446-450.
diarylalkanes. Z . Phys. Chem. N.F. 1976,101, 267-276. (350) Castellan, A.; Lacoste, J.-M.; Bow-Laurent, H. Study of non-
(325) Hayashi,T.;Suzuki,T.;Mataga, N.; Sakata, Y.; Misumi,S. Solvent- conjugated bichromophoric system, the so-called jaw photochro-
induced polarization phenomena in the excited state of composite mic materials. Part I. Photocyclomerization and fluorescence of
systems with identical halves. 1. Effects of solvent medium on the bis-santhrylmethyl ethers. J. Chem. SOC.,Perkin Trans. 2 1979,
fluorescencespectra of 1,2-dianthrylethanes. J . Phys. Chem. 1977, 411-419.
81,42&423. (351) Desvergne, J.-P.; Bitit, N.; Castellan, A.; Bow-Laurent, H. Study
(326) Anderson, B. F.; Ferguson, J.; Morita, M.; Robertson, G. B. 1,2- of non-conjugated bichromophoric system. 111. The photocy-
Di(9-anthry1)ethane. Crystal and molecular structure of the clomerization of 9-(1-naphthylmethy1oxy)-methylanthracene and
photoisomer. Conformational effects in the photophysics and 9-(2-furylmethyloxy)-methylanthracene.Interest of the CHrO-
photochemistry. J . Am. Chem. SOC.1979,101, 1832-1840. CH? link. J. Chem. SOC.,Perkin Trans. 2 1983, 109-114.
(327) Itoh, M.; Fuke, K.; Kobayashi, S. Direct observation of intramo- (352) Desvergne, J.-P.; Castellan, A.; Bow-Laurent, H.New intramo-
lecular anthracene excimer in 1,3-dianthrylpropane. J. Chem. Phys. lecular exciplexesbetween polynuclear aromatic hydrocarbons and
1980, 72, 1417-1418. head-to-head us head-to-tail photodimerization of mesoeubetituted
(328) Dunand, A.; Ferauaon, J.; Robertson, G. B. Solid state photo- anthracenes. Tetrahedron Lett. 1981,22, 3529-3532.
chemistry and ph&physicsof 1,3-di(9-anthryl)propanein i&single (353) Fages, F.; Desvergne,J.-P.; Bouas-Laurent, H.Bul1. SOC.Chim.Fr.
crystal. Chem. Phys. 1980,53, 215-223. 1985,959-964.
(329) Hara, K.; Katou, Y.; Osugi, J. Excimer fluorescence of 1,2-di(9- (354) Bokobza,L.; Pajot,E.; Monnerie, L.; Bouas-Laurent, H.; Castellan,
anthryl)ethane, 1,3-di(9-anthryl)propane,and 9,g-bianthryl a t high A. A new and convenient fluorescence molecule for probing
pressures. Bull. Chem. Soc. Jpn. 1983,56, 1308-1313. molecularmotionsin bulk polymers: 10,1(Y-diphenyl-bis-9-anthrylnthryl-
(330) Castellan, A.; Desvergne, J.-P.;Lesclaux, R.; Soulignac, J.4. New methyloxide (Diphant). Polymer 1981,22, 13W1311.
insight into the fluorescence properties of l,a-bis(g-anthryl)- (355) De Schryver, F. C.; Demeyer, K.; Huybrechts, J.; Bow-Laurent,
ethanes: temperature dependence and conformational effects in H.; Castellan, A. Intramolecular excimer fluorescence of Di(g-(lO-
dilute methylcyclohexane solutions. Chem. Phys. Lett. 1984,106, pheny1)anthryl methyl) ethers with various chain lengths. J.
117-123. Photochem. 1982,20,341-354.
(331) Scholes, G. D.; Ghiggino, K. P.; Wilson, G. Excimer geometries in (356) Becker, H.-D.; Andemon, K. Spectroscopic and photochemical
bichromophoric molecules: a theoretical and experimental study properties of diastereomeric a,-disubetituted bis[(g-anthryl)-
of 1,2-(bis-9-anthryl)-ethane.J. Chem. Phys. 1991,155,127-141. methyl] ethers. J. Org. Chem. 1982,47,354-358.
(332) Ikeda, T.; Lee, B.; Tazuke, S.; Takenaka, A. Time-resolved (357) Becker,H.-D.;Patrick,V.A.;Skelton,B.W.;White,A.H.Mol&
observation of excitation hopping between two anthryl moieties geometry of diastereomeric bis[a-(9-anthryl)ethyll ethers. A u t .
attached to both ends of alkanes: Simulation based on confor- J . Chem. 1985,38,1417-1423.
mational analysis. J . Am. Chem. SOC. 1990,112,4650-4656. (358) h t h , H. D. The beginnings of organic photochemistry. Angew.
.~ De Schrwer. F. C.: Anand. L.: Smeta. G.: Switten. J. PhotoDo-
(333)
I
Chem., Int. Ed. Engl. 1989,28,1193-1207.
lymerizaiion. IV. Photopolberimtion of bisanthraknes. Poljm. (359) (a) Fritzeche, J. Bull. Cl. Phys.-Math. Acad. Imper. Sci. St.-
Lett. 1971,9, 777-780. Pktersbourg. 1858, 16, 150-158. J. Prakt. Chem. 1868, 73, 282-
(334) De Schmer, F. C.; De Brackeleire, M.; Toppet, S.;Van Schoor, M. 292. Ann. Chem.Pharm. 1859,109 [Neue Reihel33,247-250. (b)
Photochemistry of non-conjugated bichromophoric systems. Pho- Fritzeche, M. C . R. Skances Acad. Sci. 1858,47, 723-724.
tocyclomerization of 1,l and 2,2 linked dianthracenes. Tetra- (360) (a) Fritzeche, M. Bull. SOC.Chim. Paris 1867, 8, 195-197. (b)
hedron Lett. 1973, 12153-12156. Fritzeche, J.Bul1. Acad. Imper. Sci. St.-Pktersbourg,1868,12,152-
(335) Boens, N.; De Brackelaire, M.; Huybrechts, J.; De Schryver, F. C. 154. (c) Fritzache, J. Z.Chem. 1868 11, (N.F. 4) 57.
Photochemistry of nonconjugated bichromophoric systems; the (361) Dumas, J. Ann. Chim. Phys. 1832,2,50, 183-197.
intermediacy of excimers in the intramolecular cycloaddition of (362) Laurent, A. Ann. Chim. Phys. 1837,2,66, 136-213.
polymethylene-bis-2-anthroates.Z . Phys. Chem. N.F.1976,101, (363) Anderson, Th. On the constitution of anthracene or paranaph-
417-428. thaline, and some of its products of decomposition. Trans.R. SOC.
(336) De Schryver, F. C.; Boens, N.; Huybrechta, J.; Daemen, J.; De Edinburgh, 1861, Vol. XXII, Part 111, 681-690; J. Chem. SOC.
Brackeleire, M. Photochemistry of bichromophoric compounds: London, 1862,15,44-51; Ann. Chem. Pharm. 1862,46,294-308.
Scope and expectations. Pure Appl. Chem. 1977,49,237-247. (364) Limpricht, H. Ann. Chem. Pharm. 1866,139, 303-327.
(337) De Schryver, F. C.; Boens, N.; Put, J. Excited state behavior of (365) (a) Berthelot, M. Bull. SOC.Chim. Paris 1867, 7, 43-53. (b)
some bichromophoricsystem. Advances inPhotochemistry,Pitts, Berthelot, M. Bull. SOC.Chim. Paris 1867,8,225. (c) Berthelot,
J. N., Jr., Hammond, G. S., Gollnick, K., Eds.; Interscience M. Bull. SOC. Chim.Paris 1867,8,226-259. (d) Berthelot, M. C .
Publishers: New York, 1977; Vol. 10, pp 359-465. R. Seances Acad. Sci. 1867,65,507-511. (e) Berthelot, M. Ann.
(338) Fox, M. A.; Britt, P. F. Photophysics and photochemistry of bis- Chem. Pharm. 1867, V (Supplementband), 372-377.
2-(9-anthryl)ethylglutarate.Photochem.Photobiol.1990,51,129- (366) Graebe, C.; Liebermann, C. Ber. Dtsch. Chem. Ges. 1868,1,49-51.
138. (367) Fritzeche, M. C . R. Skances Acad. Sei. 1867,64, 1035-1037.
(339) Chandross, E. A.; Schiebel, A. H. Reversible intramolecular (368) (a) Fritzache, J. Bull. Acad. Imper. Sci. St. Pktersbourg, 1869,13,
photocycloaddition of naphthalene to anthracene. J . Am. Chem. 144-168: J.Prakt. Chem. 1868.105.129-150. Ib) Fritzache. J. Bull.
SOC.1973, 95,611-612. Acad. Imper. Sci. St. Pktersbourg, 1869, 13,631-548. J: Prakt.
(340) Chandross, E. A.; Schiebel, A. H. Absorption and exciplex emission Chem. 1869,106, 274-293.
spectra of the naphthalene-anthracene sandwichpair. J.Am. Chem. (369) Fritzeche, M. C. R. Skances Acad. Sci. 1868,67, 1105-1106.
SOC.1973,95, 1671-1672. (370) (a) Graebe. C.: Liebermann. C. Ber. Dtsch. Chem. Ges. 1869.2.14.
(341) Ferguson,J.; Mau, A. W.-H.; Puza,M. Photoreactionsof anthracene (b) Graek, C.; Liebermann, C. Ann. Chem. Pharm. 1870, .VII
and naphthalene: intramolecular cycloaddition of l-(g-anthryl)- (Supplementband), 257-322.
3-(l-naphthyl)propane. Mol. Phys. 1974,28, 1457-1466. (371) Barbier, Ph. A. C. R. Skances Acad. Sci. 1874, 79, 121-125.
(342) Ferguson, J.; Mau, A. W.-H. A spectroscopic study of the inter- (372) (a) Graebe, C. Ber. Dtsch. Chem. Ges. 1872, 5, 861-863. (b)
molecular photodimerization of 1-(9-anthry1)-3-(l-naphthyl)pro- Ostermayer, E.; Fittig, R. Ber. Dtsch. Chem. Ges. 1872,5,933-937.
pane. Mol. Phys. 1974,28, 1467-1472. (373) Hayduck, M. Ann. Chem. Pharm. 1873,167, 177-186.
(343) Ferguson, J.; Mau, A. W.-H.; Whimp, P. 0. 1-(9-Anthryl)-3-(1- (374) Armstrong, H. E. The structure of cycloid hydrocarbons. Proc.
naphthybpropane. Crystal and molecular structure of the pho- Chem. Soc. 1890,6,101-105.
toisomer. Photophysics and photochemistry of the two isomers. (375) von Auwers, K. Ber. Dtsch. Chem. Ges. 1920,53,941-944.
J. Am. Chem. SOC.1979,101, 2370-2377. (376) Ingold, C. K. Introduction to Structure in Organic Chemistry. G.
(344)Mataga, N.; Yao, H.; Okada,T. Picosecond laser photolysisstudied Bell and Sons Ltd.: London, 1956; pp 169-170.
on dimer model systems in relation to photosynthetic charge (377) Fritzache, M. C . R. Skances Acad. Sci. 1862,54,91&912.
separation processes. Tetrahedron, 1989, 45, 4683-4692. (378) Wintarstain, A.; SchBn, K. Naturwissenschaften 1994, 22, 237-
(345) Daney, M.; Vanucci, C.; Desvergne, J.-P.; Castellan, A.; Bouas- 238.
Laurent, H. Photochemistry of bichromophoric systems. Silicon (379) Weigert, F. The fluorescenceof hydrocarbons and of their mixtures
guided g,lOl,2anthracene photodimerization in bis(9-anthry1)- with naphthacene. Trans. Faraday SOC.1940,36,1033-1035.
dimethylsilane. Tetrahedron Lett. 1985,26, 1505-1508. (380) Bow-Laurent, H.; Castellan, A. 4+4 Photoaddition: C r d
(346) Sakurai, H.; Sakamoto, K.;Nakamura, A.;Kira, M. Photochemistry dimers of anthracene and tetracene; the pure dimer of 9,lO-
of di(9-anthry1)dimethylsilane and -germane. Chem. Lett. 1985, dimethylanthracene. J . Chem. SOC.,Chem. Commun. 1970,1648-
497-498. 1649.
(347) Felix, G.; Lapouyade, R.; Bouas-Laurent, H.; Clin, B. Photocy- (381) Ferguaon, J.; Mau, A. W.-H.; Whimp, P. 0. Photodimer of 9,lO-
clization of bis(9-anthryl) 1,1,3,3-tetramethyldiailoxane,unsym- dimethylanthracene and tetracene. Crystal and molecular struc-
metrical photodimerization of the anthracene ring. Tetrahedron ture, photophysics, and photochemistry. J . Am. Chem. SOC. 1979,
Lett. 1976, 2277-2278. 101,2363-2369.
172 Chemical Revlews, 1993, Vd. 93,No. 1 Beckor

(382) Lapouyade, R.; Nourmamode, A.; Bow-Laurent, H. Tetrahedron A photocroee-linkingapproach usinganthraceneaea photoactiwble
1980,36,2311-2316. group. FEBSLett.1984,174,1-5. (b)TaLu,K.;Sd,H.;Kimura,
(383) Yamamoto, S.; Grellmann, K.-H. The adiabatic photodissociation 5.; Imanishi, Y. Effects of lipid structure on energy t r a d e r from
of the anthracene-tetracene photodimer. Chem. Phys. Lett. 1982, carbamyl to anthryl groups in a lipid bilayer. Biophys. Chem.
92,533-540. 1992,44, 187-198.
(384) Bjameson, D.W.; Petersen, N. 0. The photochemistry of naph-
thacene in solution. J. Photochem. Photobiol. A Chem. 1992,63, (389) Kumar, C. V.; Asuncion,E. H. Sequence dependent energytrane.fer
327-335. fromDNAtoasimp1earomaticchophore. J. Chem.Soc.,Chem.
(385) von Biinau, G.;Wolff, T. Photochemistry in surfactant solutions. Commun. 1992, 470-472.
Aduances in Photochemktry; Volman, D.H., Hammond, G.S., (390) Naruta, Y .;Maruyama, K. High oxygen-evolvingactivity of rigidly
Gollnick, K., Eds.;Interscience Publishers: New York, 1988; Vol. linked manganeae(II1) porphyrin dimers. A functional model of
14, pp 273-331.
(386) Ueno, A.; Morikawi, F.; Iwama, Y.; Suzuki, I.; Osa, T.; Ohta, T.; manganese catalase. J. Am. Chem. SOC.1991,113,3695-3696.
Nozoe, S. y-Cyclodextrin template method for controlling stere- (391) Seaaler, J. L.; Mody, T. D.;Ford, D.A,; Lynch, V. A nonaromatic
ochemistryof bimolecularinteractions and reactions. J.Am. Chem. expanded porphyrin derived from anthracene - A macrocyclewhich
SOC.1991,113,7034-7036. unexpectedly binds anions. Angew. Chem., Znt. Ed. Engl. 1992,
(387) Tamaki, T.; Kawanishi, Y.; Seki, T.; Sakuragi, M. Triplet sensi- 31,452-455.
tization of anthracene photodimerization in y-cyclodextrin. J.
Photochem. Photobiol. A: Chem. 1992,65, 313-320. (392) Baumgarten, M.; MUer, U.; Bohnen, A.; M u e n , K. Oligo(9,lO-
(388) (a) de Bony, J.; Martin, G.;Welby, M.;Tocanne, J. F. Evidence for anthrylenes), organic compounds with stable high-spin states.
homogeneouslateral distribution of lipids in a bacterial membrane. Angew. Chem., Int. Ed. Engl. 1992, 31, 448-451.