Malonic Acid Derivatives On Duty As Electron-Withdrawing Units in Push-Pull Molecules

DOI: 10.1002/ejoc.
201700070 Full Paper
Donor–Acceptor Systems
Malonic Acid Derivatives on Duty as Electron-Withdrawing Units
in Push–Pull Molecules
Milan Klikar,[a] Veronika Jelínková,[a] Zdeňka Růžičková,[b] Tomáš Mikysek,[c] Oldřich Pytela,[a]
Miroslav Ludwig,[a] and Filip Bureš*[a]
Abstract: Based on the 2-(N-piperidinyl)thiophene central do- electron-withdrawing abilities of malonic acid acceptors were
nor, 32 model push–pull molecules with systematically varied examined both by experiment including X-ray analysis, differen-
malonic acid-derived peripheral acceptors have been prepared. tial scanning calorimetry, electrochemistry, and UV/Vis absorp-
Further property tuning has been achieved by modifying the tion spectroscopy, and by DFT calculations. Details of the struc-
π-linker and the structural arrangement (linear vs. quadrupolar ture–property relationships have been elucidated. According to
D–π–A systems). Malonic acid derivatives such as cyanoacetic the increasing electron-withdrawing ability, the widely used
acid, malondinitrile, diethyl malonate, Meldrum′s acid, and N,N′- malonic acid acceptor units can be ordered: diethyl malonate ≤
dibutyl(thio)barbituric acid as well as 1,3-diketo analogues di- cyanoacetic acid < malondinitrile < Meldrum's acid < dimedone
medone and indan-1,3-dione were employed as acceptor moie- ≤ N,N′-dibutylbarbituric acid < indan-1,3-dione ≤ N,N′-dibutyl-
ties. Knoevenagel condensation with four thiophene aldehydes thiobarbituric acid.
afforded the target chromophores in satisfactory yields. The
Introduction Organic push–pull chromophores currently constitute an in-

tensively investigated class of π-conjugated systems, which has
Malonic acid (MA) was prepared for the first time by oxidation
found many applications across chemistry and material scien-
of malic acid by French chemist V. Dessaignes in 1858.[1] Since
ces.[5] The unique and peculiar properties of push–pull mol-
this early experiment, malonic acid and its derivatives became
ecules such as color, (hyper)polarizability, dipolar character, and
a well-known and widely studied class of organic compounds.
extraordinary linear and nonlinear optical behavior, are mainly
They are extensively used in industry, especially in pharmaceuti-
induced by intramolecular charge transfer (ICT) from the elec-
cals, agrochemicals, vitamins, dyes, adhesives, and fragrances.[2]
tron donor through the π-linker to the electron acceptor.[6] Op-
A common feature of MA derivatives is the high reactivity of
tical properties, HOMO–LUMO gap, dipole moments, hyper-
the central methylene bridge. The acidity of the CH2, induced
polarizability coefficients, etc. are mainly dictated by the extent
by two neighboring carbonyl groups, allow these compounds
of the ICT. In push–pull molecules, the aforementioned funda-
to easily undergo alkylation, arylation, aldol and Knoevenagel
mental properties can easily be tuned by the type of used elec-
condensations, and MA derivatives are also often utilized in the
tron donors and acceptors, length and composition of the π-
construction of heterocycles.[3] Knoevenagel condensation is
linker, and overall chromophore arrangement.[7] The high im-
one of the main synthetic tools used for introducing MA deriva-
portance of D-π-A systems can clearly be demonstrated by their
tives into the structure of push–pull chromophores. This reac-
wide applications as active substances in organic electronics,
tion between a carbonyl compound and a substance bearing
molecular optics,[8] and semiconductors.[9] For many decades,
an active methylene group is generally acid- or base-cata-
MA derivatives have been widely used as electron-withdrawing
lyzed.[4]
parts of push–pull chromophores. Their popularity can be as-
cribed to their commercial availability, low price, easy incorpo-
[a] Institute of Organic Chemistry and
ration into the chromophore, and relatively high electron-with-
Technology, Faculty of Chemical Technology, University of Pardubice, drawing character. Moreover, a suitable choice of MA derivative
Studentská 573, Pardubice, 53210, Czech Republic enables facile fine-tuning of target chromophore properties. Ac-
E-mail: [email protected] cording to the functional groups, MA derivatives can be divided
http://bures.upce.cz
into three general subgroups: (1) nitriles (e.g., cyanoacetic acid,
[b] Department of General and Inorganic Chemistry, Faculty of Chemical
Technology, University of Pardubice, ethyl cyanoacetate, and malondinitrile, (2) esters (e.g., dialkyl
Studentská 573, Pardubice 53210, Czech Republic malonate and Meldrum′s acid), and (3) imides [e.g., (thio)barbi-
[c] Department of Analytical Chemistry, Faculty of Chemical Technology, turic acid].
University of Pardubice,
Studentská 573, Pardubice 53210, Czech Republic
Malonic acid and cyanoacetic acid are currently privileged
Supporting information and ORCID(s) from the author(s) for this article are precursors for the construction of chromophores for dye-sensi-
available on the WWW under https://doi.org/10.1002/ejoc.201700070. tized solar cells (DSSC).[10] The principal advantage of cyano-
Eur. J. Org. Chem. 2017, 2764–2779 2764 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Paper
acetic acid can be seen in combining both withdrawing (-CN) ticular MA-derivatives can be roughly estimated according to
and anchoring (-COOH) abilities. Malondinitrile,[11] as a starting their pKa values.
compound for the formation of the dicyanovinyl (DCV) with- The electron-withdrawing strength of the acceptors as well
drawing unit, is one of the most popular electron-acceptor moi- as the influence of the branching and extension of the π-linker
eties ever. For instance, the DCV unit has been extensively stud- were investigated by electrochemistry, UV/Vis absorption spec-
ied by Diederich et al.[12] and recently reviewed by us.[13] More tra, DSC, X-ray analysis, and DFT quantum chemical calculations.
recently, we have prepared a series of model tripodal molecules Based on the measured and calculated data, structure–property
with peripheral cyano acceptors including a DCV moiety. This relationships have been elucidated and are discussed.
study clearly demonstrates a strong withdrawing ability of the
DCV unit compared with other used cyano acceptors.[14] In con-
trast, dialkyl malonates have rarely been employed in the con- Results and Discussion
struction of push–pull chromophores.[15] This is probably due
to the weak withdrawing ability caused by +M effects of the We designed and prepared 32 push–pull chromophores (31
alkoxy groups. Meldrum′s acid as a cyclic ester of malonic acid new) bearing eight electron-acceptor parts as well as extended
is likewise rarely used in push–pull chromophores, but it has and branched π-conjugated systems based on 2-(N-piper-
been used in some D-π-A systems.[16] On the other hand, barbi- idinyl)thiophene (PIT) donor/linker (Figure 1). The precursors of
turic acid and its thio analogue are very popular MA derivatives the particular MA derivative were cyanoacetic acid (CAA),
with notable electron-withdrawing strength. These acceptor malondinitrile (MDN), diethyl malonate (DEM), Meldrum′s acid
moieties are abundant in many (mero)cyanine dyes,[17] nonlin- (MEL), N,N′-dibutylbarbituric acid (DBB), N,N′-dibutyl-2-thio-
ear optic chromophores,[18] solvatochromic[19] and near-infrared barbituric acid (DBTB), dimedone (DMD), and indan-1,3-dione
probes,[20] dyes for DSSCs,[21] and supramolecular complexes (IND).
based on multiple H-bonding interactions.[22] In 2013, we util- According to structural features, the target chromophores 1–
ized N,N′-dibutylbarbituric acid as a powerful and well-soluble 8 can be divided in four subseries a–d. The chromophore num-
acceptor moiety of push–pull chromophores with a systemati- ber specifies type of the acceptor(s): 1 = CAA, 2 = MDN, 3 =
cally elongated π-linker.[23] Recently, we have also focused on DEM, 4 = DMD, 5 = MEL, 6 = DBB, 7 = DBTB, and 8 = IND.
multipodal push–pull molecules end-capped with DCV or N,N′- Labels a–d indicates length of the π-linker (ethenylene in series
dibutylbarbituric unit(s).[24] This preceding research inspired us a and c; but-1,3-dienylene in series b and d) as well as degree
to study and critically compare the electron-withdrawing abili- of branching (linear a and b; branched c and d).
ties of acceptor units based on various MA derivatives. It is quite
surprising that, to our knowledge, no attempts have been made
to systematically compare the electron-withdrawing strength of Synthesis
a wide range of malonic derivatives. Beside pure MA derivatives,
this study also involves two additional 1,3-diketo analogues In general, all target push–pull chromophores 1–8 were pre-
such as dimedone and indan-1,3-dione. Whereas dimedone, pared through Knoevenagel condensation. Cyanoacetic
representing an analogue of Meldrum′s acid, was used very acid (CAA), malondinitrile (MDN), diethyl malonate (DEM), Mel-
rarely in organic (opto)electronics,[25] indan-1,3-dione proved to drum′s acid (MEL), dimedone (DMD), and indan-1,3-dione (IND)
be a very powerful acceptor, for instance in our recent T-shaped are commercially available. The remaining acceptor precursors,
chromophores.[26] The electron-withdrawing abilities of the par- namely N,N′-dibutylbarbituric acid (DBB) and N,N′-dibutyl-2-
Figure 1. Target linear/branched chromophores with eight withdrawing units based on MA derivatives and its analogues.
Eur. J. Org. Chem. 2017, 2764–2779 www.eurjoc.org 2765 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Paper
Scheme 1. Synthesis of N,N′-dibutyl(thio)barbituric acids DBB and DBTB.
thiobarbituric acid (DBTB) were synthesized by acid/base cata- pared through alternative twofold Wittig elongation of 9c by
lyzed condensation of N,N′-dibutyl(thio)ureas 12 and 14 with using commercially available phosphonium salt 19.[28] Subse-
malonic acid or diethyl malonate according to Scheme 1. De- quent hydrolysis of the formed diacetal intermediate yielded
tailed synthetic procedures are given in the Supporting Infor- 9d with 74 % yield. Detailed synthetic procedures and charac-
mation. terization (including X-rays) of all four aldehydes 9a–d are given
Scheme 2 shows overall preparations of PIT aldehydes. PIT in the Supporting Information.
(17), as a fundamental D/π building block, was prepared by the With PIT aldehydes 9a–d in hand, we carried out their Knoev-
reaction of thiophene-2-thiol 15 with piperidine 16 with 53 % enagel condensations with the aforementioned MA derivatives
yield.[27] Its direct lithiation with nBuLi at –78 °C and subse- (Scheme 3). Given that the particular MA derivatives exhibit var-
quent reaction with N,N-dimethylformamide (DMF) afforded lin- ious basicity/nucleophilicity and aldehydes 9a–d possess differ-
ear aldehyde 9a with 66 % yield.[28] A similar reaction sequence ent reactivity/electrophilicity, the reaction conditions had to be
with 3-(N,N-dimethylamino)acrolein 18 afforded extended alde- optimized. In some reactions, a generally well-working and very
hyde 9b with 67 % yield. PIT also underwent Vilsmeier–Haack convenient CH2Cl2/Al2O3 system[30,23,12–14] had to be replaced
formylation with the DMF/POCl3 system.[29] In contrast to avail- with a CH3CN/piperidine version. The Knoevenagel reactions of
able reports,[28,29] we have isolated only dialdehyde 9c irrespec- 9a–d with parent MA provided completely insoluble com-
tive of the amount of DMF/POCl3 used. This twofold formylation pounds. The particular reaction conditions are listed in the
provided branched dialdehyde 9c in satisfactory yield of 68 %. Experimental section. The attained yields do not show any
However, all attempts to perform similar Vilsmeier–Haack for- notable trends, they rather represent an intersection of acid-
mylation of 17 with 18 resulted in a very exothermic reaction base properties of the starting materials as well as the separa-
and decomposition. Hence, extended dialdehyde 9d was pre- tion techniques used.
Scheme 2. Construction of PIT aldehydes 9a–d.
Full Paper
Scheme 3. General synthetic pathway to chromophores 1–8 through Knoevenagel condensation.
X-ray Analysis by slow diffusion of hexane into the corresponding dichloro-

methane solution. The ORTEP plots of PIT aldehydes are shown
Crystals of PIT aldehydes 9a–d as well as target chromophores in Figure S1 in the Supporting Information, for target chromo-
2c, 4a, 5b, and 8a–b suitable for X-ray analysis were obtained phores see Figure 2. These plots confirm the proposed molec-
Figure 2. X-ray molecular representations of chromophores 2c (a), 4a (b), 5b (c), 8a (d), and 8b (e).
Full Paper
ular structures as well as arrangement of the particular alde- Table 1 lists all measured melting points (Tm) and temperatures
hyde/chromophore in the solid state. The ORTEP plot of 9c of thermal decompositions (Td). All DCS curves are given in the
further confirms that the observed twofold Vilsmeier–Haack Supporting Information. The measured melting points range
formylation takes place selectively at the C3 and C5 positions from 62 to 261 °C. The temperature of decomposition was esti-
of the PIT. mated within the range of 171–303 °C.
The MA-derived acceptor units in 2c, 4a, 5b, and 8a–b are Except 1a, all linear chromophores in series a exhibited a
almost perfectly co-planar with the central thiophene moiety. very sharp endothermic peak of melting. Chromophore 3a is a
Regardless of the used π-linker (ethenylene or but-1,3-dienyl- viscous oil that decomposed directly at 269 °C followed by a
ene), the dihedral angles between these two moieties do not melting of the decomposed residue. For 4a and 7a, the exother-
exceed 10° (generally 1–3°). This allows efficient overlap of the mic peaks of decomposition were observed shortly after melt-
π-electron clouds across the whole π-system and facilitates ICT ing, whereas 1a, 2a, 5a, 6a, and 8a were stable in the liquid
between the donor and the acceptor. Branching of the chromo- phase for an additional 40–150 °C above their melting point.
phore caused only minor deviation of the piperidine ring. Except 3b, bearing a DEM acceptor unit (Tm = 62 °C), very sharp
A variation of the C–C bond lengths within the thiophene peaks of melting were found for compounds in series b (Tm =
ring in a range from typical C=C double bond to ca 1.42 Å has 155–213 °C). In contrast to 1b–3b, and 6b, decomposition of
been revealed from the X-ray data. This can be attributed to 4b, 5b, 7b, and 8b followed immediately their melting.
elongated thiophene bonds, whereas the rest of the C–C, C–N The compounds in branched series c and d showed complex
and C–O (multiple) bonds are localized at appropriate places thermal behavior. Compounds 2c and 6c exhibited sharp melt-
with lengths similar to the reported values. In this respect, the ing peaks followed by gradual decomposition, whereas the
extent of the ICT can be assessed by calculating bond length melting of 4c, 5c, 7c, and 8c was immediately overset to exo-
alternation within the central thiophene ring. Its quinoid char- thermic decompositions. For most compounds in series c the
acter/aromaticity can easily be determined by the Bird index subsequent decomposition peaks were also observed. Oily 3c
(I5).[31] Whereas the Bird index of unsubstituted thiophene is 66, exhibited similar thermal behavior to that of 3a. Whereas 2d
thiophene rings in 2c, 4a, 5b, and 8a–b possess I5 within the and 5d decomposed immediately after melting, 6d and espe-
range of 59 to 63. This implies less aromaticity and higher quin- cially 3d were also stable in the liquid phase. In contrast, com-
oid character of the thiophene rings due to the ICT. However, pounds 1d, 4d, 7d, and 8d decomposed directly without melt-
the PIT donor connected to a powerful T-shaped, indan-1,3- ing.
dione-derived acceptor can be polarized even further, with I5 = Desorption of the residual/crystalline solvents were observed
58.[26b] for compounds 1b, 1c, 1d, 5b, 6d, and 8d. Moreover, 5c and
The supramolecular arrangement of 2c, 4a, 5b, and 8a–b 6d also showed solid–solid transitions at 125 and 140 °C, re-
reveals 2D-layered array structures due to extensive π–π stack- spectively.
ing supported by numerous noncovalent C–H···negative atom
From the measured thermal properties, we can conclude the
interactions.
following outcomes: (1) Elongation of the π-linker by embed-
ding an additional double bond decreases Td (e.g., linear series
b vs. a; Figure 3). (2) The measured Td values are very close
(ΔTd = 5–40 °C) for pairs of compounds with the same acceptors
Thermal Properties
in series c and d (Figure 3). (3) In general, the linear compounds
1a–8a and 1b–8b always showed melting peaks, whereas the
The thermal behavior of compounds 1–8 was studied by differ-
branched 1c–8c and 1d–8d often underwent additional ther-
ential scanning calorimetry (DSC). Figure 3 shows thermograms
mal processes or decomposed directly without melting. (4) The
of representative compounds 7a–d (DBTB chromophores) and
lowest melting points were determined for 3b (62 °C) and 3d
(123 °C) with DEM acceptor bearing ethyl chains. In general,
alkyl chains hamper crystallization and significantly affect the
melting points. (5) In contrast, compounds end-capped with
DEM unit(s) (3a–d) exhibited the highest average Td values.
(6) Similarly, CAA-, MDN-, and IND-terminated compounds (1a–
d, 2a–d, and 8a–d) significantly resisted thermal decomposi-
tion. (7) MEL-substituted 5a–d possess higher Td compared with
structurally similar DMD 4a–d (effect of the oxygen atoms).
(8) The effect of a chalcogenide atom can distinguish DBB (6a–
d) and DBTB (7a–d) derivatives. The sulfur atom in DBTB in-
creases the melting point and generally decreases Td compared
with DBB oxygen analogues.
With respect to these conclusions, the highest melting point
and decomposition temperature were observed for 2d (Td =
Figure 3. Representative DSC curves of compounds 7a–d (DBTB chromo- 261 °C) and 2a (Td = 303 °C) end-capped with MDN acceptor
phores) determined with a scanning rate of 3 °C/min under N2. unit(s).
Full Paper
Table 1. Summarized thermal, electrochemical, and linear optical properties of chromophores 1–8.
[a] [b] [c] [c]
Compound Tm Td E1/2(ox1) E1/2(red1) ΔE[c] EHOMO[e] ELUMO[e] λmaxA[f ] εmaxA·103
[°C] [°C] [V] [V] [V] [eV] [eV] [nm/eV] (M–1 cm–1)
1a 130 205 –[g] –[g] – – – 436/2.84, 459/2.70[h] 28.8/45.9[h]
2a 143 303 0.95[d] –1.29 2.24 –5.30 –3.06 464/2.67 57.9
3a – 269 0.72 –1.63 2.35 –5.07 –2.72 430/2.88 36.1
4a 205 217 0.83 –1.36 2.19 –5.18 –2.99 488/2.54 81.4
5a 184 232 0.94[d] –1.30[d] 2.24 –5.29 –3.05 468/2.65 90.5
6a 172 251 0.88[d] –1.28[d] 2.16 –5.23 –3.07 486/2.55 110.6
7a 216 231 0.94[d] –1.15[d] 2.09 –5.29 –3.20 508/2.44 120.8
8a 182 243 0.80 –1.21[d] 2.01 –5.15 –3.14 515/2.41 105.1
1b 155 217 –[g] –[g] – – – 468/2.65, 533/2.33[h] 17.5/23.7[h]
2b 155 254 0.67 –1.02 1.69 –5.02 –3.33 551/2.25 73.3
3b 62 258 0.53 –1.33 1.86 –4.88 –3.02 466/2.66 35.2
4b 169 179 0.59 –1.03 1.62 –4.94 –3.32 594/2.09 109.8
5b 213 218 0.67 –0.96 1.63 –5.02 –3.39 572/2.17 142.1
6b 148 207 0.64 –0.95 1.59 –4.99 –3.40 592/2.09 142.1
7b 175 186 0.69 –0.82 1.51 –5.04 –3.53 614/2.02 174.9
8b 204 215 0.56[d] –0.93 1.49 –4.91 –3.42 619/2.00 123.0
1c – 264 –[g] –[g] – – – 398/3.12, 448/2.77[h] 14.7/14.1[h]
2c 215 222 1.24 –0.92 2.16 –5.59 –3.43 472/2.63 30.3
3c – 298 0.96[d] –1.45[d] 2.41 –5.31 –2.90 386/3.21 28.3
4c 204 209 0.97 –1.02 1.99 –5.32 –3.33 497/2.49 42.7
5c 199 205 1.15[d] –0.90[d] 2.05 –5.50 –3.45 477/2.60 41.1
6c 127 171 1.04[d] –0.90 1.94 –5.39 –3.45 527/2.35 39.4
7c 172 179 1.09[d] –0.65 1.74 –5.44 –3.70 519/2.39 87.9
8c 243 254 1.00 –0.85 1.85 –5.35 –3.50 556/2.23 48.3
1d – 250 –[g] –[g] – – – 433/2.86, 465/2.67[h] 17.8/19.1[h]
2d 261 264 0.85 –0.85 1.70 –5.20 –3.50 522/2.38 36.8
3d 123 286 0.71 –1.21 1.92 –5.06 –3.14 423/2.93 37.1
4d – 214 0.76 –0.85 1.61 –5.11 –3.50 583/2.13 29.2
5d 235 244 0.85 –0.75 1.60 –5.20 –3.60 579/2.14 47.8
6d 178 212 0.79 –0.75 1.54 –5.14 –3.60 598/2.07 54.8
7d – 184 0.85 –0.52 1.37 –5.20 –3.83 656/1.89 68.0
8d – 242 0.75 –0.74 1.49 –5.10 –3.61 585/2.12 43.2
[a] Tm = melting point (the point of intersection of a baseline and a tangent of thermal effect = onset). [b] Td = thermal decomposition (pyrolysis in N2
atmosphere). [c] E1/2(ox1) and E1/2(red1) are half-wave potentials of the first oxidation and reduction, respectively; all potentials are given vs. SCE; ΔE = E1/2(ox1)
– E1/2(red1). [d] Reversible process. [e] –EHOMO/LUMO = E1/2(ox1/red1) + 4.429 (Ref.[32]). [f] Measured in CH3OH/CH2Cl2, 24:1 at concentration 10–5 M. [g] Not
measurable. [h] AcOH (5 μL) was added to measured solutions.
Electrochemistry unit(s) as well as the π-linker length (Table 1). Whereas the first
oxidation most likely takes place at the PIT donor, the first re-
Electrochemical measurements of chromophores 1–8 were car-
duction is situated on the withdrawing moiety and the adjacent
ried out in N,N-dimethylformamide containing 0.1 M Bu4NPF6 in
π-linker. All half-wave potentials of the first oxidation and re-
a three-electrode cell by cyclic voltammetry (CV) and rotating-
duction were further recalculated to the energies of the HOMO
disk voltammetry (RDV). The working electrode was a glassy
and LUMO (EHOMO/LUMO), respectively.[32] Hence, further discus-
carbon disk (2 mm in diameter) for CV and RDV experiments.
sion will be given in terms of these quantities and their differen-
Saturated calomel electrodes (SCE) were used as reference and
ces ΔE because these fit better to the purposes of this article.
auxiliary electrodes, separated by a bridge filled with support-
The energy level diagram of averaged values of the EHOMO/LUMO
ing electrolyte and Pt wire, respectively. All potentials are given
for the given quartet of chromophores with the same acceptor
vs. SCE. Table 1 lists the acquired data, and representative CV
unit is shown in Figure 4.
diagrams of compounds 2c, 3d, 4a, 5b, 6c, 7d, and 8a are given
in the Supporting Information. Chromophores 1a–d with CAA As a general trend, the EHOMO values gradually decreased in
acceptor(s) were not measurable by using the employed elec- the order b → d → a → c. Hence, extension of the π-linker
trochemical techniques. shifts the HOMO levels to more positive values most signifi-
The values of the half-wave potentials of the first oxidation cantly (b vs. a, or d vs. c). Chromophore branching has the
and reduction E1/2(ox1) and E1/2(red1) were recorded within the opposite effect and further reduces the EHOMO values (c vs. a,
range of 0.53 to 1.15 and –1.63 to –0.52 V, respectively. The or d vs. b). The lowest/highest averaged HOMO level belong to
first oxidation and reduction are typical one-electron processes, chromophores 2/3 bearing MDN/DEM acceptor units.
followed by subsequent oxidations and reductions, and are On average, the ELUMO values decreased in order a → b → c
clearly a function of the number and type of the used acceptor → d. In contrast to the HOMO levels, the ELUMO is shifted to
Full Paper
The longest wavelength absorption maxima of chromophores

1–8 ranged from 386 to 656 nm with corresponding εmax values
of 15 to 175 × 103 M–1 cm–1.
Figure 4. Energy level diagram of averaged values of the electrochemical

(black) and DFT calculated (red) energies EHOMO/LUMO for the particular series
of MA-derived withdrawing units.
more negative values upon both extension of the π-system and

branching in the chromophore. Hence, the lowest/highest aver-
aged ELUMO values were measured for chromophore 7/3 with
DBTB/DEM acceptor units. Given that the first reduction and
the LUMO are localized on the acceptor moieties of 1–8, the
energies ELUMO can be used to order the acceptor units as: DEM
< DMD ≤ MDN ≤ MEL ≤ DBB < IND < DBTB.
The difference between the first oxidation and reduction po-
tentials/HOMO and LUMO levels (electrochemical gap, ΔE) rep-
resents a direct way of evaluating the extent of the ICT across
all withdrawing units and chromophores. Given that the elec-
tron-donating part (PIT) remained unaltered in all chromo-
phores, the changes seen in the EHOMO/LUMO can be ascribed
to the structural changes in: (1) The length of the π-linker; its
extension always reduces the ΔE. (2) The chromophore branch-
ing, which also reduces the ΔE; this effect is especially pro-
nounced when going from linear series a to branched series c
and less for series b and d in which the effect of the π-linker
elongation dominates. (3) The HOMO–LUMO gap in 1–8, which
is mostly dictated by the withdrawing unit appended to the PIT
donor. According to decreasing ΔE values, we can order the
acceptor units as: DEM < MDN < MEL ≤ DMD < DBB < IND <
DBTB (Figure 4).
Hence, chromophores 7d (1.37 eV), 8b, and 8d (both
1.49 eV) bearing DBTB and IND acceptor units possess the nar-
rowest ΔE. In contrast, DEM-terminated molecules 3a (2.35 eV)
Figure 5. Representative, mathematically smoothed (ref.[33]) UV/Vis absorption
and 3c (2.41 eV) possess the largest HOMO–LUMO gaps.
spectra of DBB chromophores 6a–d (a) and 1b–8d in CH3OH/CH2Cl2 (24:1)
at concentration 1 × 10–5 M.
One Photon Absorption

Linear chromophores in series a and b always exhibit a single
All target chromophores 1–8 are intensely colored solids or oils CT band, whereas the spectra of branched molecules in series
with a color ranging from yellow to blue (see Figure S10 in c and d feature two more or less developed CT bands (Fig-
the Supporting Information), most of them show no emissive ure 5a). This reflects two conjugated pathways between both
properties. Hence, optical absorption properties were examined acceptors and the PIT central donor and their quadrupolar
by UV/Vis spectroscopy. The longest wavelength absorption nature. According to the Frenkel exciton model, the excited
maxima λmax and molar absorption coefficients εmax are sum- state of a quadrupolar molecule is split into two bands that are
marized in Table 1. Selected absorption spectra are shown in energetically positioned at +V and –V (where V is the inter-
Figure 5; for complete listing see the Supporting Information. branch coupling) relative to the excited state of the parent di-
Full Paper
polar molecule.[34] For quadrupolar branched molecules, both media with acetic acid (Figure 6), resulted in significant redshift
bands are one-photon allowed (observable), with the low- of the spectra as the COOH remained undissociated. (4) Cyclic
energy lying band possessing greater oscillator strength (larger MEL proved to be a much stronger acceptor than linear DEM
εmax). This is also the case for chromophores 6a/6c and 6b/6d (lactone vs. ester). Hence, cyclic MA-derivatives are generally
(Figure 5a). For instance, 6a possesses a single CT band with stronger electron acceptors. (5) O→C replacement in MEL led
λmax = 486 nm and εmax = 110.6 × 103 M–1 cm–1, whereas the to DMD (ester vs. ketone) with improved withdrawing ability
spectrum of its quadrupolar analogue 6c features two bands (counterproductive saturation of the carbonyls by alkoxy
at 428 and 527 nm with εmax = 24.3 and 39.4 × 103 M–1 cm–1, groups in MEL). (6) Chalcogenide O→S replacement as in DBB
respectively. Figure 5a also clearly demonstrates the effect of vs. DBTB significantly affects the properties of both acceptors.
π-linker elongation. When going from 6a to 6b or from 6c to The latter proved much stronger. (7) O→N replacements as in
6d (insertion of one double bond in each branch), the positions CAA vs. MDN or MEL vs. DBB enhances the withdrawing power;
of the longest absorption maxima shifts bathochromically with therefore, MDN and DBB are stronger acceptors than CAA and
Δλmax of 106 and 71 nm, respectively. MEL, respectively. (8) When comparing 1,3-diketones DMD and
The trends seen by electrochemical measurements are also IND, the latter showed much stronger withdrawing ability be-
obeyed in electronic absorption spectra. Namely, extension of cause the fused benzene ring allowed enlarged conjugation.
the π-linker of the chromophore reduces the optical gap (1240/
λmax; see Table 1). Chromophore branching has no clear trends
across the whole series because two peaks for quadrupolar Quantum Chemical Calculations
chromophores in series c and d were observed. Hence, both
redshifts and slight blueshifts were observed (Table 1). Alterna- Spatial and electronic properties of all target chromophores
tion of the acceptor units affects the optical properties of 1–8 were investigated at the DFT level by using the Gaussian
chromophores 1–8 most significantly. For instance, a gradual W09 package.[35] The geometries of molecules 1–8 were opti-
replacement of the DEM acceptor in 3b (λmax = 466 nm) up to mized by using the DFT B3LYP/6-311G(d,p) method. Energies
DBTB or IND shifted the λmax to 614 (7b) and 619 (8b) nm, of the HOMO and LUMO, their differences, ground-state dipole
respectively (Δλmax ca. 150 nm, Figure 5b). Thus, a suitable moments μ and first hyperpolarizabilities β were also calculated
choice of MA acceptor allows tuning of the optical gap by on the DFT B3LYP/6-311++G(2d,p) level. The calculated data are
about 0.7 eV. Figure 6 compares the averaged optical gaps of summarized in Table 2.
all MA derivatives. Considering the λmax-derived optical gaps, The calculated energies of the HOMO and LUMO of 1–8
the withdrawing abilities of the MA derivatives showed the range from –6.69 to –5.27 eV and from –3.57 to –1.92 eV, re-
same trend as seen by the ΔE values (see their correlation in spectively. They are clearly a function of the branching, exten-
Figure S55) with the order: DEM ≤ CAA < MDN < MEL < DMD sion of the π-linker, and type of the attached acceptor moiety.
≤ DBB < IND ≤ DBTB. The calculated HOMO–LUMO gaps (ΔEDFT ) are generally slightly
wider than those obtained by electrochemistry; however, the
trends within the whole series of molecules are clearly pre-
served (Figure 4). Moreover, the calculated HOMO–LUMO differ-
ences correlate tightly with both electrochemical and optical
gaps (Figure S56–S57) and, therefore, the used DFT method can
be considered as a reasonable tool describing electronic prop-
erties of 1–8. For instance, the narrowest ΔEDFT of 2.47 eV was
calculated for chromophore 7d with DBTB acceptor moiety,
which is similar to the electrochemical outcome. In general,
the averaged ΔEDFT values of 1–8 decrease in the order: DEM
> CAA ≈ MDN ≈ MEL > DMD ≈ DBB > IND > DBTB, which
resembles the order deduced from the electrochemical and op-
tical properties.
The HOMO and LUMO localizations in representative
chromophores 5b and 8d are shown in Figure 7. Complete list-
ing is given in the Supporting Information. Molecules in linear
series a and b, e.g., 5b, possess the HOMO and the HOMO-1
Figure 6. Comparison of averaged optical gaps (1240/λmax) for the series of
MA-derived withdrawing units. * Acetic acid was added. localized predominantly on the piperidinyl donor and partially
in the alternating positions. The LUMO is spread over the MEL
acceptor part, adjacent π-linker, and partially also on the piper-
The following structure-withdrawing property relationships idinyl residue. The LUMO+1 is localized on the thiophene cen-
can be deduced among the particular MA-acceptors: (1) DEM tral part. Branched chromophores in series c and d, e.g., 8d,
is the weakest electron acceptor, DBTB and IND are the most showed very similar localization of the HOMO and HOMO-1,
powerful. (2) MDN proved to be a stronger acceptor unit than whereas the LUMO is spread mostly over the IND acceptor ap-
CAA. (3) The withdrawing behavior of CAA strongly depends pended on the remote branch. The second branch closer to the
on the extent of the COOH dissociation. Acidification of the piperidinyl donor is occupied by the LUMO+1. This distribution
Full Paper
Table 2. DFT calculated parameters of chromophores 1–8.
Compound EHOMO[a] ELUMO[a] ΔEDFT μ[a] β × 10–30[a] Compound EHOMO[a] ELUMO[a] ΔEDFT μ[a] β × 10–30[a]
(eV) (eV) (eV) (D) (esu) (eV) (eV) (eV) (D) (esu)
1a –5.75 –2.46 3.29 10.9 34 1c –6.40 –3.14 3.26 12.5 47
2a –5,89 –2.67 3.22 12.8 38 2c –6.69 –3.41 3.28 9.4 43
3a –5.39 –1.92 3.47 7.1 52 3c –5.73 –2.08 3.65 2.3 53
4a –5.54 –2.31 3.23 6.8 57 4c –5.86 –2.74 3.12 3.4 92
5a –5.71 –2.39 3.32 8.3 41 5c –6.17 –2.89 3.28 5.1 67
6a –5.65 –2.41 3.24 9.2 51 6c –5.99 –2.89 3.10 5.9 86
7a –5.69 –2.63 3.06 10.9 30 7c –6.05 –3.19 2.86 6.9 370
8a –5.52 –2.47 3.05 6.9 134 8c –5.76 –2.89 2.87 4.7 295
1b –5.57 –2.76 2.81 15.4 194 1d –5.99 –3.29 2.70 14.9 659
2b –5.66 –2.88 2.78 15.1 182 2d –6.39 –3.57 2.82 8.7 304
3b –5.27 –2.25 3.02 10.4 198 3d –5.74 –2.73 3.01 7.8 288
4b –5.34 –2.61 2.73 8.6 319 4d –5.60 –3.00 2.60 5.5 3343
5b –5.48 –2.68 2.80 10.2 233 5d –5.82 –3.13 2.69 7.0 906
6b –5.44 –2.70 2.74 11.1 299 6d –5.74 –3.12 2.62 9.0 2316
7b –5.49 –2.88 2.61 13.1 368 7d –5.82 –3.35 2.47 11.3 829
8b –5.34 –2.69 2.65 8.5 707 8d –5.74 –3.08 2.66 4.0 28222[b]
[a] Calculated at the DFT B3LYP/6-311++G(2d,p) level. [b] Likely to be an overestimated value (repeated calculations always with the same result).
of the LUMO orbitals is a common feature of branched push– Polarizabilities of the chromophores 1–8 have also been
pull molecules.[14,34] Surprisingly, chromophores 7a–d have the evaluated by calculating the first hyperpolarizabilities β
HOMO localized on the sulfur and oxygen atoms of the DBTB (Table 2). Excluding 8d as an outlier, the calculated β values
acceptor. range from 30 to 3343 × 10–30 esu. Compared to linear chromo-
phores 1a–8a (β = 30–134 × 10–30 esu), extension of the π-
linker as in 1b–8b resulted in significant improvement of the
first hyperpolarizability β up to 182–707 × 10–30 esu. Similar and
even pronounced trend can be seen when comparing series c
and d. Branched chromophores in series c and d possess up to
one order of magnitude higher β values than the correspond-
ing linear analogues in series a and b. From the MA-derived
acceptor moieties, the DBTB and IND impart the strongest ICT
into the molecule, which also reflects their generally highest
calculated NLO coefficients in series a–c. However, in the
branched and most extended series d, the highest β values
were calculated for 4d and 6d (and 8d), bearing 1,3-diketo
(DMD and IND) or DBB acceptors. Hence, indan-1,3-dione and
(thio)barbituric acids seems to be the most powerful acceptors
from the whole series of push–pull molecules.
Conclusions
To study the withdrawing ability of six malonic acid derivatives
and two of its analogues, new model push–pull chromophores
have been designed and synthesized. First, a straightforward
Figure 7. HOMO/HOMO-1 (red) and LUMO/LUMO+1 (blue) localizations in 5b reaction path towards four PIT aldehydes has been developed.
(a) and 8d (b). These aldehydes underwent smooth Knoevenagel condensa-
tion with eight different MA-derivatives to afford 32 mostly new
The calculated ground-state dipole moments range from 2.3 push–pull molecules 1–8 in four series a–d. These chromo-
to 15.4 D. In general, the highest values were calculated for phores have systematically varied peripheral acceptor moiety,
chromophores with CAA (1a–d), MDN (2a–d), and DBTB (7a– structural arrangement, and length of the π-linker. Detailed
d) acceptors (9–15 D). In contrast, chromophores with diketo structure–property relationships have been elucidated by con-
acceptors such as DMD (4a–d) and IND (8a–d) showed signifi- sidering both experimental (thermal, electrochemical, and opti-
cantly diminished μ values (2–8 D). Extension of the π-linker cal) and calculated data.
generally increased the dipole moment, whereas branching has Molecular structures of all PIT aldehydes 9a–d as well as five
rather the opposite effect. target chromophores 2c, 4a, 5b, and 8a–b were confirmed by
Full Paper
X-ray analysis, which revealed essentially planar structures, high calorimetry DSC with a Mettler-Toledo STARe System DSC 2/700
quinoid character of the central thiophene ring, and extensive equipped with FRS 6 ceramic sensor and cooling system (HUBERT
π–π stacking in the solid state. TC100-MT RC 23). Thermal behavior of the target chromophores
were measured in open aluminous crucibles under N2 inert atmos-
DSC analysis showed that π-linker extension decreased the
phere. DSC curves were determined with a scanning rate of 3 °C/
thermal robustness, branching mostly caused direct decompo-
min within the range 25–450 °C. Melting point and temperature of
sition without melting, and variation of the peripheral with- decomposition were determined as intersection of the baseline and
drawing moiety affected the thermal properties of 1–8 accord- tangent of the peak (onset point). Elemental analyses were carried
ing to its nature. Hence, the highest thermal robustness has out with a Fison EA 1108 instrument. 1H and 13C NMR spectra were
been observed for MDN-terminated molecules as well as for recorded at 400 and 100 MHz, respectively, with a Bruker AVANCE
CAA-, DEM-, and IND-derivatives. 400 instrument or at 500 and 125 MHz, respectively, with a Bruker
The electrochemical and UV/Vis absorption optical measure- AscendTM 500 at 25 °C. Chemical shifts are reported in ppm relative
ments revealed the same trends and structural features influ- to the signal of Me4Si. The residual solvent signal in the 1H and 13C
NMR spectra was used as an internal reference (CDCl3 δ = 7.25 and
encing the fundamental properties of target chromophores 1–
77.23 ppm; CD2Cl2 δ = 5.32 and 54.00; [D6]DMSO δ = 2.55 and
8. Namely, the π-linker extension and gradual chromophore
39.51; D2O δ = 4.80). Apparent resonance multiplicities are de-
branching reduces both electrochemical and optical gaps. How- scribed as s (singlet), d (doublet), dd (doublet of doublet), t (triplet),
ever, the HOMO/LUMO levels and resulting gaps are predomi- q (quartet), and m (multiplet), apparent coupling constants of multi-
nantly dictated by the composition, electronic, and spatial na- plets (3J or 4J) are given in Hz. Thiophene and aromatic indan-1,3-
ture of the used acceptor. A replacement of the atoms (O→C, dione signals are marked as th and ind, respectively. IR spectra were
O→N, and O→S) within the acceptor unit significantly improves recorded as neat by using HATR adapter with a Perkin–Elmer FTIR
its electron-withdrawing ability. Cyclic acceptors proved to be Spectrum BX spectrometer. Mass spectra were measured with a GC–
stronger than linear analogues. Extended π-conjugation (e.g., MS configuration comprised of an Agilent Technologies 6890N gas
IND) further enhances withdrawing behavior. chromatograph equipped with a 5973 Network MS detector (EI
70 eV, mass range 33–550 Da). High-resolution MALDI MS spectra
The aforementioned conclusions are fully supported by the
were measured with a MALDI mass spectrometer LTQ Orbitrap XL
DFT calculations. The calculated data correlates tightly with the (Thermo Fisher Scientific, Bremen, Germany) equipped with nitro-
electrochemical and optical properties. gen UV laser (337 nm, 60 Hz). The LTQ Orbitrap instrument was
Hence, based on the experimental results as well as calcu- operated in positive-ion mode over a normal mass range (m/z
lated properties, the MA-derived acceptors can be ordered as: 50–2000) with resolution 100 000 at m/z = 400. The survey crystal
DEM ≤ CAA < MDN < MEL < DMD ≤ DBB < IND ≤ DBTB. positioning system (survey CPS) was set for the random choice of
In general, the MA-derived acceptors can be classified in four shot position by automatic crystal recognition. 2,5-Dihydroxy-
subgroups: (1) Weak (DEM), (2) moderate (CAA, MDN), (3) pow- benzoic acid (DHB), 2-[(E)-3-(4-tert-butylphenyl)-2-methylprop-2-en-
erful (MEL, DMD, DBB), and (4) very strong (IND, DBTB). ylidene]propanedinitrile (DCTB) and 9-aminoacridine (9-AA) were
used as a matrix. Mass spectra were averaged over the whole MS
The main goal of this work was to investigate and critically
record for all measured samples. The absorption spectra were meas-
compare the withdrawing ability of commonly used MA-de- ured with a Hewlett–Packard 8453 spectrophotometer in CH3OH/
rived acceptors. Therefore, a wide range of target MA-chromo- CH2Cl2, 24:1 at concentration of 1 × 10–5 M. Voltammetric measure-
phores has been synthesized based on the PIT donor, which ments were performed by using a potentiostat PGSTAT 128N
allowed proper evaluation of averaged experimental and theo- (AUTOLAB, Metrohm Autolab B.V., Utrecht, The Netherlands) oper-
retical results. We believe that the deduced outcomes may ated with NOVA 1.11 software.
serve as a useful guide to conveniently select a suitable MA General Procedure for Knoevenagel Condensation of 9a–d with
derivative for the given D-π-A system with desired optoelec- Cyanoacetic Acid (GP1): Aldehyde 9a–b (1 mmol) and cyanoacetic
tronic behavior. acid (1.5 mmol) or dialdehyde 9c–d (1 mmol) and cyanoacetic acid
(3 mmol), were dissolved in CH3CN (10 mL) and piperidine (0.5 mL;
5 mmol) was added dropwise. The reaction mixture was heated to
reflux for 90 min, the solvents were removed in vacuo and the
Experimental Section
residue was dissolved in CH2Cl2 (20 mL). Acetic acid (about 1 mL)
General Methods: The preparation and characterization of N,N′- was added dropwise and the reaction mixture was stirred at 25 °C
dibutyl(2-thio)barbituric acids, PIT 17, and aldehydes 9a–d are for 30 min. The solvent was partially evaporated in vacuo and the
given in the Supporting Information. The remaining acceptor pre- residue was purified by column or flash chromatography and then
cursors (CAA, MDN, DEM, MEL, DMD, IND) as well as starting com- recrystallized from CH2Cl2/CH3OH.
pounds 10, 11, 13, 15, 16, 18, and 19 are commercially available.
General Procedure for Knoevenagel Condensation Catalyzed by
All commercial chemicals, reagents and solvents were purchased
Al2O3 (GP2): Aldehyde 9a–b (1 mmol) and acceptor precursor
from Sigma Aldrich, Acros and TCI and were used as received.
(1.2 mmol) or dialdehyde 9c–d (1 mmol) and acceptor precursor
THF was dried with a PuresolvTM micro solvent purification system.
(2.5 mmol), were dissolved in CH2Cl2 (25 mL) and Al2O3 (5 or
Lithiation and Wittig reactions were carried out in flame-dried flasks
10 mmol, Brockmann II–III) was added. The reaction mixture was
under argon. Column chromatography was carried out with silica
stirred at 25 °C for 18 h then filtered and the solvent was evapo-
gel 60 (particle size 0.040–0.063 mm, 230–400 mesh; Merck) and
rated in vacuo. The crude product was purified by column chroma-
commercially available solvents. Thin-layer chromatography (TLC)
tography.
was conducted on aluminum sheets coated with silica gel 60 F254,
obtained from Merck, with visualization by a UV lamp (254 or 360 General Procedure for Knoevenagel Condensation Catalyzed by
nm). Thermal properties were measured by differential scanning Piperidine (GP3): Aldehyde 9a–b (1 mmol) and acceptor precursor
Full Paper
(1.2 mmol) or dialdehyde 9c–d (1 mmol) and acceptor precursor Chromophore 2b: The title compound was synthesized from alde-
(2.5 mmol), were dissolved in CH3CN (25 mL) and a few drops of hyde 9b (222 mg) and malondinitrile (80 mg) by following general
piperidine were added. The reaction mixture was heated to reflux procedure GP2. Yield: 200 mg (74 %); violet solid; m.p. 155 °C; Rf =
for 18 h. The solvents were removed in vacuo and the crude prod- 0.7 (SiO2; CH2Cl2). C15H15N3S (269.36): calcd. C 66.88, H 5.61, N 15.60,
uct was purified by column chromatography. S 11.90; found C 66.82, H 5.70, N 15.59, S 11.79. 1H NMR (500 MHz,
Chromophore 1a: The title compound was synthesized from alde- CDCl3, 25 °C): δ = 1.66–1.75 (m, 6 H, CH2), 3.39–3.41 (m, 4 H, CH2),
hyde 9a (195 mg) by following general procedure GP1. Yield: 6.07 (d, J = 4.5 Hz, 1 H, CHth), 6.42 (dd, J1 = 12, J2 = 14 Hz, 1 H,
215 mg (82 %); terracotta solid; m.p. 130 °C; Rf = 0.6 (SiO2; CH2Cl2/ CH), 7.16–7.19 (m, 2 H, CHth+CH), 7.29 ppm (d, J = 12 Hz, 1 H, CH).
13
CH3OH, 10:1). 1H NMR (500 MHz, [D6]DMSO, 25 °C): δ = 1.66 (s, 6 H, C NMR (125 MHz, CDCl3, 25 °C): δ = 23.67, 25.20, 51.53, 106.02,
CH2), 3.50–3.51 (m, 4 H, CH2), 6.50 (d, J = 4.5 Hz, 1 H, CHth), 7.79 114.32, 114.46, 116.48, 123.81, 140.28, 143.36, 159.02, 167.42 ppm.
(d, J = 4.5 Hz, 1 H, CHth), 8.12 ppm (s, 1 H, CH). 13C NMR (125 MHz, FTIR (HATR): ν̃ = 2919, 2852, 2189, 1578, 1514, 1421, 1326, 1218,
[D6]DMSO, 25 °C): δ = 23.11, 24.69, 50.75, 104.58, 119.47, 119.84, 1166, 1127, 1058, 963 cm–1. HR-MALDI-MS (DHB): m/z calcd. for
141.89, 144.06, 166.39, 166.64 ppm. FTIR (HATR): ν̃ = 2920, 2852, C15H15N3S [M]+ 269.09812; found 269.09854.
2359, 2201, 1648, 1571, 1496, 1402, 1238, 1197, 1174, 1132, 1099, Chromophore 2c: The title compound was synthesized from di-
1012, 888, 758, 661 cm–1. HR-MALDI-MS (9-AA): m/z calcd. for aldehyde 9c (222 mg) and malondinitrile (165 mg) by following
C13H13N2O2S [M – H]+ 261.06922; found 261.07157. general procedure GP2. Yield: 261 mg (82 %); burgundy red solid;
Chromophore 1b: The title compound was synthesized from alde- m.p. 215 °C; Rf = 0.8 (SiO2; EtOAc/Hex, 1:1). C17H13N5S (319.38):
hyde 9b (221 mg) by following general procedure GP1. Yield: calcd. C 63.93, H 4.10, N 21.93, S 10.04; found C 63.70, H 4.15, N
110 mg (38 %); red-black solid; m.p. 155 °C; Rf = 0.6 (SiO2; CH2Cl2/ 21.89, S 9.87. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 1.77–1.79 (m, 2
CH3OH, 10:1). 1H NMR (500 MHz, [D6]DMSO, 25 °C): δ = 1.60–1.65 H, CH2), 1.83–1.86 (m, 4 H, CH2), 3.55–3.57 (m, 4 H, CH2), 7.48 (s, 1
(m, 6 H, CH2), 3.30–3.32 (m, 4 H, CH2), 6.19 (d, J = 4 Hz, 1 H, CHth), H, CH), 7.65 (s, 1 H, CH), 8.08 ppm (s, 1 H, CH). 13C NMR (125 MHz,
6.33 (dd, J1 = 12, J2 = 15 Hz, 1 H, CH), 7.13 (d, J = 4 Hz, 1 H, CHth), CDCl3, 25 °C): δ = 23.35, 25.67, 57.04, 113.51, 113.75, 114.35, 114.45,
7.31 (d, J = 14.5 Hz, 1 H, CH), 7.70 ppm (d, J = 12 Hz, 1 H, CH). 13C 114.91, 122.61, 139.60, 149.05, 150.31, 173.92 ppm. FTIR (HATR): ν̃ =
NMR (125 MHz, [D6]DMSO, 25 °C): δ = 23.18, 24.59, 50.79, 69.81, 2923, 2208, 1538, 1502, 1442, 1350, 1225, 1198, 853 cm–1. HR-
104.48, 116.19, 118.79, 124.42, 134.53, 137.55, 150.28, 162.21, MALDI-MS (DHB): m/z calcd. for C17H13N5S [M]+ 319.08862; found
165.83 ppm. FTIR (HATR): ν̃ = 2834, 2361, 2210, 1584, 1441, 1312, 319.08904.
1223, 1146, 1074, 964, 888, 763 cm–1. HR-MALDI-MS (DCTB): m/z Chromophore 2d: The title compound was synthesized from di-
calcd. for C15H17N2O2S [M + H]+ 289.10052; found 289.17153. aldehyde 9d (276 mg) and malondinitrile (165 mg) by following
Chromophore 1c: The title compound was synthesized from di- general procedure GP2. After column chromatography, the product
aldehyde 9c (223 mg) by following general procedure GP1. Yield: was heated to reflux with hexane (20 mL). The precipitate was fil-
290 mg (81 %); dark orange solid. Rf = 0.9 (SiO2; CH2Cl2/CH3OH, 1:1). tered off, washed with EtOAc (10 mL), and dried. Chromophore 2d
1
H NMR (400 MHz, D2O, 25 °C): δ = 1.65–1.74 (m, 6 H, CH2), 3.36– is sparingly soluble in common chlorinated solvents. Yield: 242 mg
3.38 (m, 4 H, CH2), 7.86 (s, 1 H, CH), 7.90 (s, 1 H, CH), 7.96 ppm (s, (65 %); black solid; m.p. 261 °C; Rf = 0.8 (SiO2; CH2Cl2). C21H17N5S
1 H, CH). 13C NMR (125 MHz, D2O, 25 °C): δ = 22.99, 25.14, 55.96, (371.46): calcd. C 67.90, H 4.61, N 18.85, S 8.63; found C 66.92, H
99.36, 102.94, 115.30, 119.17, 119.66, 122.06, 137.44, 143.72, 145.03, 4.47, N 18.89, S 8.04. 1H NMR (500 MHz, CD2Cl2, 25 °C): δ = 1.70–
169.16, 169.36, 171.17 ppm. FTIR (HATR): ν̃ = 3404, 2210, 1603, 1444, 1.80 (m, 6 H, CH2), 3.35–3.36 (m, 4 H, CH2), 6.70 (dd, J1 = 12, J2 =
1357, 1338, 1288, 1183, 789 cm–1. HR-MALDI-MS (9-AA): m/z calcd. 15 Hz, 1 H, CH), 6.90 (dd, J1 = 11.5, J2 = 15 Hz, 1 H, CH), 7.13 (d, J =
for C17H14N3O4S [M – H]+ 356.06995; found 356.07267. 15 Hz, 1 H, CH), 7.26 (d, J = 14.5 Hz, 1 H, CH), 7.42 (s, 1 H, CHth),
7.50 (d, J = 12 Hz, 1 H, CH), 7.55 ppm (d, J = 12 Hz, 1 H, CH). 13C
Chromophore 1d: The title compound was synthesized from di-
NMR (125 MHz, CD2Cl2, 25 °C): δ = 23.94, 25.95, 56.39, 79.22, 79.63,
aldehyde 9d (276 mg) by following general procedure GP1. Yield:
113.07, 114.92, 115.00, 119.75, 120.59, 121.58, 128.00, 134.92,
278 mg (68 %); red-brown solid. Rf = 0.9 (SiO2; CH3OH). 1H NMR
141.47, 142.28, 159.57, 160.77, 170.12 ppm. FTIR (HATR): ν̃ = 2352,
(400 MHz, [D6]DMSO, 25 °C): δ = 1.53–1.54 (m, 2 H, CH2), 1.70 (s, 4
2205, 1559, 1475, 1345, 1217, 1153, 975 cm–1. HR-MALDI-MS (DHB):
H, CH2), 3.00–3.03 (m, 4 H, CH2), 6.51 (dd, J1 = 11.6, J2 = 14.8 Hz, 1
m/z calcd. for C21H17N5S [M]+ 371.11992; found 371.12018.
H, CH), 6.84 (dd, J1 = 11.6, J2 = 15.2 Hz, 1 H, CH), 6.97 (d, J = 15.2 Hz,
1 H, CH), 7.26 (d, J = 14.8 Hz, 1 H, CH), 7.39 (s, 1 H, CHth), 7.57 (d, Chromophore 3a: The title compound was synthesized from alde-
J = 11.6 Hz, 1 H, CH), 7.65 ppm (d, J = 11.6 Hz, 1 H, CH). 13C NMR hyde 9a (195 mg) and diethyl malonate (192 mg) by following gen-
not measurable due to a low solubility of 1d in common deuterated eral procedure GP3. Yield: 165 mg (49 %); yellow-orange viscous oil;
solvents. FTIR (HATR): ν̃ = 2359, 2215, 1594, 1365, 1298, 1154, 980, Rf = 0.6 (SiO2; Hex/EtOAc, 2:1). C17H23NO4S (337.43): calcd. C 60.51,
789 cm–1. HR-MALDI-MS (DCTB): m/z calcd. for C21H19N3O4S [M]+ H 6.87, N 4.15, S 9.50.; found C 60.52, H 7.00, N 4.20, S 9.49. 1H NMR
409.10908; found 409.11051. (400 MHz, CDCl3, 25 °C): δ = 1.29 (t, J = 9 Hz, 3 H, CH3), 1.36 (t, J =
9 Hz, 3 H, CH3), 1.61–1.71 (m, 6 H, CH2), 3.28–3.31 (m, 4 H, CH2),
Chromophore 2a: The title compound was synthesized from alde-
4.23 (q, J = 9 Hz, 2 H, CH2), 4.34 (q, J = 9 Hz, 2 H, CH2), 5.99 (d, J =
hyde 9a (195 mg) and malondinitrile (79 mg) by following general
5.5 Hz, 1 H, CHth), 7.18 (d, J = 5.5 Hz, 1 H, CHth), 7.77 ppm (s, 1 H,
procedure GP2. Yield: 200 mg (82 %); orange solid; m.p. 143 °C; Rf =
CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 14.38, 14.54, 23.81, 25.19,
0.75 (SiO2; CH2Cl2). C13H13N3S (243.33): calcd. C 64.17, H 5.39, N
51.18, 60.98, 61.36, 103.89, 111.80, 120.42, 139.48, 141.20, 166.23,
17.27, S 13.18; found C 64.09, H 5.43, N 17.19, S 12.94. 1H NMR
167.15, 167.57 ppm. FTIR (HATR): ν̃ = 2936, 2855, 1694, 1589, 1514,
(500 MHz, CDCl3, 25 °C): δ = 1.68–1.75 (m, 6 H, CH2), 3.46–3.48 (m,
1441, 1376, 1239, 1055, 887, 856, 756 cm–1. HR-MALDI-MS (DHB):
4 H, CH2), 6.13 (d, J = 4.5 Hz, 1 H, CHth), 7.33 (s, 1 H, CHth), 7.39 ppm
m/z calcd. for C17H24NO4S [M + H]+ 338.14206; found 338.14377.
(s, 1 H, CH). 13C NMR (125 MHz, CD2Cl2, 25 °C): δ = 23.84, 25.62,
52.06, 105.88, 116.97, 117.75, 119.68, 145.68, 148.72, 170.75 ppm. Chromophore 3b: Aldehyde 9b (221 mg) and diethyl malonate
FTIR (HATR): ν̃ = 2918, 2190, 1575, 1513, 1487, 1446, 1402, 1266, (160 mg) were dissolved in CH3CN (25 mL), Al2O3 (510 mg; 5 mmol)
1078, 769 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C13H13N3S [M]+ and a few drops of piperidine were added. The reaction mixture
243.08247; found 243.08273. was heated to reflux for 4 h, subsequently stirred at 25 °C for 16 h,
Full Paper
filtered, and the solvent was evaporated in vacuo. The crude prod- 1356, 1243, 1188, 1122, 1091, 1018, 890, 758 cm–1. HR-MALDI-MS
uct was purified by column chromatography (SiO2, CH2Cl2/acetone, (DHB): m/z calcd. for C18H24NO2S [M + H]+ 318.15223; found
100:5). Yield: 280 mg (77 %); dark-red solid; m.p. 62 °C; Rf = 0.9 318.15252.
(SiO2; CH2Cl2/acetone, 100:5). C19H25NO4S (363.47): calcd. C 62.78,
Chromophore 4b: Aldehyde 9b (221 mg) and dimedone (168 mg)
H 6.93, N 3.85, S 8.82; found C 62.74, H 7.11, N 3.82, S 8.71. 1H NMR
were dissolved in CH2Cl2 (15 mL) and a few drops of piperidine
(500 MHz, CDCl3, 25 °C): δ = 1.29 (t, J = 7 Hz, 3 H, CH3), 1.36 (t, J = were added. The reaction mixture was stirred at 25 °C for 16 h, the
7 Hz, 3 H, CH3), 1.59–1.62 (m, 2 H, CH2), 1.67–1.71 (m, 4 H, CH2), solvent was evaporated in vacuo, and the crude product was puri-
3.23–3.25 (m, 4 H, CH2), 4.23 (q, J = 7 Hz, 2 H, CH2), 4.32 (q, J = fied by column chromatography (SiO2, CH2Cl2/EtOAc, 1:1). Yield:
7 Hz, 2 H, CH2), 5.93 (d, J = 4 Hz, 1 H, CHth), 6.74 (dd, J1 = 12, J2 =
85 mg (25 %); violet solid; m.p. 169 °C; Rf = 0.8 (SiO2; CH2Cl2/EtOAc,
15 Hz, 1 H, CH), 6.92 (d, J = 4 Hz, 1 H, CHth), 7.03 (d, J = 14.5 Hz, 1 1:1). C20H25NO2S (343.48): calcd. C 69.93, H 7.34, N 4.08, S 9.34;
H, CH), 7.50 ppm (d, J = 12 Hz, 1 H, CH). 13C NMR (125 MHz, CDCl3, found C 69.99, H 7.51, N 4.02, S 9.11. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 14.47, 14.53, 23.81, 25.16, 51.43, 61.01, 61.04, 104.24,
25 °C): δ = 1.04 (s, 6 H, CH3), 1.64–1.73 (m, 6 H, CH2), 2.44 (s, 4 H,
117.25, 118.93, 125.91, 133.86, 139.59, 148.01, 163.29, 165.79,
CH2), 3.38–3.40 (m, 4 H, CH2), 6.07 (d, J = 4.5 Hz, 1 H, CHth), 7.19
166.21 ppm. FTIR (HATR): ν̃ = 2920, 2850, 2368, 1690, 1577, 1522,
(d, J = 4.5 Hz, 1 H, CHth), 7.40 (d, J = 13.5 Hz, 1 H, CH), 7.79 (d, J =
1436, 1314, 1204, 1137, 1049, 1027, 749 cm–1. HR-MALDI-MS (DHB): 12.5 Hz, 1 H, CH), 7.86–7.91 ppm (m, 1 H, CH). 13C NMR (125 MHz,
m/z calcd. for C19H26NO4S [M + H]+ 364.15771; found 364.15930. CDCl3, 25 °C): δ = 23.72, 25.22, 28.80, 30.59, 51.53, 106.30, 119.10,
Chromophore 3c: The title compound was synthesized from di- 122.33, 126.24, 139.92, 149.54, 152.94, 167.59, 198.37 ppm. FTIR
aldehyde 9c (222 mg) and diethyl malonate (192 mg) by following (HATR): ν̃ = 2935, 2851, 1613, 1540, 1346, 1212, 1108, 1002,
general procedure GP3. Yield: 238 mg (47 %); yellow-brown viscous 784 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C20H26NO2S [M + H]+
oil; Rf = 0.8 (SiO2; CH2Cl2/EtOAc, 20:1). C25H33NO8S (507.60): calcd. 344.16788; found 344.16822.
C 59.15, H 6.55, N 2.76, S 6.32; found C 59.27, H 6.70, N 2.61, S 6.12. Chromophore 4c: Aldehyde 9c (223 mg) and dimedone (350 mg)
1
H NMR (500 MHz, CDCl3, 25 °C): δ = 1.25–1.34 (m, 12 H, CH3), 1.57– were dissolved in CHCl3 (30 mL) and a few drops of piperidine were
1.61 (m, 2 H, CH2), 1.70–1.74 (m, 4 H, CH2), 3.14–3.17 (m, 4 H, CH2), added. The reaction mixture was heated at 40 °C for 16 h then the
4.20–4.25 (m, 4 H, CH2), 4.30–4.36 (m, 4 H, CH2), 7.22 (s, 1 H, CH), solvent was evaporated in vacuo. The crude product was dissolved
7.53 (s, 1 H, CH), 7.59 ppm (s, 1 H, CH). 13C NMR (125 MHz, CDCl3, in EtOAc (5 mL) and precipitated with hexane. The precipitate was
25 °C): δ = 14.17, 14.29, 14.32, 23.78, 25.67, 56.19, 61.46, 61.50, filtered off, purified by filtration through a short plug (SiO2, EtOAc/
61.86, 61.89, 118.65, 118.76, 121.95, 124.12, 133.93, 135.76, 136.52, Hex, 2:1), and re-precipitated again from EtOAc/hexane. The prod-
164.80, 164.91, 166.71, 166.97, 169.58 ppm. FTIR (HATR): ν̃ = 2922, uct proved unstable on SiO2. Yield: 61 mg (13 %); red-violet solid;
2851, 1616, 1540, 1417, 1348, 1137, 1110, 1051, 1002, 973, 885, m.p. 204 °C; Rf = 0.4 (SiO2; EtOAc/Hex, 2:1). C27H33NO4S (467.62):
786 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C25H33NO8S [M]+ calcd. C 67.35, H 7.11, N 3.00, S 6.66; found C 67.21, H 7.05, N 2.98,
507.19214; found 507.19402. S 6.05. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 1.07 (s, 6 H, CH3), 1.10
Chromophore 3d: Aldehyde 9d (276 mg) and diethyl malonate (s, 6 H, CH3), 1.74–1.81 (m, 6 H, CH2), 2.50 (s, 4 H, CH2), 2.56 (s, 2 H,
(400 mg) were dissolved in CH2Cl2 (15 mL), Al2O3 (510 mg; 5 mmol) CH2), 2.58 (s, 2 H, CH2), 3.62 (s, 4 H, CH2), 7.86 (s, 1 H, CH), 8.14 (s,
and a few drops of piperidine were added. The reaction mixture was 1 H, CH), 8.41 ppm (s, 1 H, CH). 13C NMR (125 MHz, CDCl3, 25 °C):
heated to reflux for 16 h, filtered, and the solvent was evaporated δ = 23.87, 26.03, 28.82, 28.84, 30.32, 30.55, 52.18, 52.58, 53.18, 54.25,
in vacuo. The crude product was purified by column chromatogra- 56.37, 119.01, 120.83, 123.00, 125.91, 141.88, 145.57, 152.68, 178.86,
phy (SiO2, EtOAc/Hex, 2:3 and CH2Cl2/EtOAc, 20:1). Yield: 302 mg 197.48, 197.50, 198.43, 198.45 ppm. FTIR (HATR): ν̃ = 2930, 2860,
(54 %); red solid; m.p. 123 °C; Rf = 0.7 (SiO2; EtOAc/Hex, 2:3). 1648, 1624, 1467, 1351, 1288, 1233, 1201, 1133, 1116, 955, 646 cm–1.
C29H37NO8S (559.67): calcd. C 62.23, H 6.66, N 2.50, S 5.73; found C HR-MALDI-MS (DHB): m/z calcd. for C27H34NO4S [M + H]+ 468.22031;
61.97, H 6.82, N 2.47, S 5.61.1H NMR (400 MHz, CDCl3, 25 °C): δ = found 468.22239.
1.29–1.38 (m, 12 H, CH3), 1.59–1.63 (m, 2 H, CH2), 1.72–1.78 (m, 4 Chromophore 4d: The title compound was synthesized from di-
H, CH2), 3.04–3.07 (m, 4 H, CH2), 4.22–4.28 (m, 4 H, CH2), 4.31–4.37 aldehyde 9d (276 mg) and dimedone (350 mg) by following general
(m, 4 H, CH2), 6.86 (dd, J1 = 11.6, J2 = 14.8 Hz, 1 H, CH), 6.93–7.02 procedure GP2. Yield: 210 mg (40 %); black solid‘ Rf = 0.85 (SiO2;
(m, 3 H, CH+CHth), 7.12 (s, 1 H, CH), 7.44 (d, J = 11.6 Hz, 1 H, CH), EtOAc/Hex, 2:1). C31H37NO4S (519.70): calcd. C 70.64, H 7.18, N 2.70,
7.48 ppm (dd, J1 = 1.6, J2 = 9.2 Hz, 1 H, CH). 13C NMR (125 MHz, S 6.17; found C 70.31, H 7.29, N 2.47, S 5.59. 1H NMR (500 MHz,
CDCl3, 25 °C): δ = 14.43, 14.50, 23.85, 25.82, 56.07, 61.41, 61.44, CDCl3, 25 °C): δ = 1.05–1.06 (2×s, 12 H, CH3), 1.67–1.69 (m, 2 H,
61.46, 121.27, 121.85, 123.03, 123.33, 124.87, 129.26, 131.13, 136.40, CH2), 1.76–1.81 (m, 4 H, CH2), 2.49–2.51 (m, 8 H, CH2), 3.29–3.31 (m,
137.70, 145.86, 145.92, 146.67, 163.62, 165.23, 165.33, 165.71, 4 H, CH2), 7.22 (d, J = 15 Hz, 1 H, CH), 7.33 (d, J = 15 Hz, 1 H, CH),
165.86 ppm. FTIR (HATR): ν̃ = 2978, 2936, 2854, 1718, 1587, 1443, 7.39 (s, 1 H, CHth), 7.74 (t, J = 12.5 Hz, 2 H, CH), 7.93 (dd, J1 = 12,
1375, 1208, 1144, 1058, 1021, 858 cm–1. HR-MALDI-MS (DHB): m/z J2 = 14.5 Hz, 1 H, CH), 8.03 ppm (dd, J1 = 12.5, J2 = 15 Hz, 1 H, CH).
calcd. for C29H37NO8S [M]+ 559.22344; found 559.22518. 13
C NMR (125 MHz, CDCl3, 25 °C): δ = 23.76, 25.65, 28.76, 30.40,
52.42, 52.47, 54.13, 55.97, 123.31, 123.41, 123.80, 126.62, 126.92,
129.75, 133.76, 145.39, 146.33, 151.39, 152.45, 168.62, 198.06,
hyde 9a (195 mg) and dimedone (168 mg) by following general
198.36, 199.16, 199.22 ppm. FTIR (HATR): ν̃ = 2934, 2865, 2359, 1642,
procedure GP3. Yield: 260 mg (82 %); orange solid; m.p. 205 °C; Rf =
1549, 1486, 1367, 1234, 1134, 973, 777 cm–1. HR-MALDI-MS (DHB):
0.6 (SiO2; CH2Cl2/EtOAc, 1:1). C18H23NO2S (317.45): calcd. C 68.10, H
m/z calcd. for C31H38NO4S [M + H]+ 520.25161; found 520.25237.
7.30, N 4.41, S 10.10.; found C 68.02, H 7.35, N 4.40, S 10.05. 1H NMR
(500 MHz, CDCl3, 25 °C): δ = 1.05 (s, 6 H, CH3), 1.71 (s, 6 H, CH2), Chromophore 5a: The title compound was synthesized from alde-
2.44 (s, 4 H, CH2), 3.55–3.56 (m, 4 H, CH2), 6.33 (d, J = 5 Hz, 1 H, hyde 9a (195 mg) and Meldrum′s acid (172 mg) by following gen-
CHth), 7.62 (d, J = 4.5 Hz, 1 H, CHth), 8.12 ppm (s, 1 H, CH). 13C eral procedure GP3 in CH2Cl2 at 25 °C. Yield: 128 mg (40 %); orange
NMR (125 MHz, CDCl3, 25 °C): δ = 23.82, 25.52, 28.82, 30.79, 51.28, solid; m.p. 184 °C; Rf = 0.4 (SiO2; Hex/EtOAc, 1:2). C16H19NO4S
52.22, 108.94, 115.40, 123.77, 143.42, 152.75, 173.70, 197.24 ppm. (321.39): calcd. C 59.79, H 5.96, N 4.36, S 9.98; found C 59.87, H 6.02,
FTIR (HATR): ν̃ = 2940, 2855, 1647, 1585, 1558, 1482, 1440, 1374, N 4.36, S 9.89. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 1.71–1.73 (m,
Full Paper
12 H, CH2+CH3), 3.55–3.56 (m, 4 H, CH2), 6.28 (d, J = 5.2 Hz, 1 H, 23.75, 25.55, 30.54, 41.03, 41.77, 51.37, 99.65, 108.25, 122.67, 146.42,
CHth), 7.56 (d, J = 4.8 Hz, 1 H, CHth), 8.22 ppm (s, 1 H, CH). 13C 151.92, 151.96, 162.85, 163.90, 174.74 ppm. FTIR (HATR): ν̃ = 2923,
NMR (125 MHz, CDCl3, 25 °C): δ = 23.77, 25.54, 27.45, 51.56, 92.97, 2856, 1632, 1470, 1411, 1248, 1155, 1084, 783 cm–1. HR-MALDI-
103.58, 107.98, 122.10, 146.56, 151.91, 163.65, 165.76, 175.00 ppm. MS (DHB): m/z calcd. for C22H32N3O3S [M + H]+ 418.21589; found
FTIR (HATR): ν̃ = 2923, 2854, 1672, 1493, 1372, 1256, 1177, 1005, 418.21567.
929, 770 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C16H20NO4S [M
Chromophore 6b: Aldehyde 9b (222 mg) and N,N′-dibutylbarbit-
+ H]+ 322.11075; found 322.13881.
uric acid (288 mg) were dissolved in 1,2-dichloroethane (20 mL) and
Chromophore 5b: The title compound was synthesized from alde- Al2O3 (255 mg; 2.5 mmol) was added. The reaction mixture was
hyde 9b (221 mg) and Meldrum′s acid (216 mg; 1.5 mmol) by fol- heated to reflux for 6 h, subsequently stirred at 25 °C for 16 h,
lowing general procedure GP2 with CH3CN at 85 °C for 48 h. Yield: filtered, and the solvent was evaporated in vacuo. The crude prod-
153 mg (44 %); violet solid; m.p. 213 °C; Rf = 0.6 (SiO2; Hex/EtOAc, uct was purified by column chromatography (SiO2, CH2Cl2/acetone,
1:2). C18H21NO4S (347.43): calcd. C 62.23, H 6.09, N 4.03, S 9.23; 60:1). Yield: 248 mg (56 %); black solid; m.p. 148 °C; Rf = 0.4 (SiO2;
found C 62.13, H 6.15, N 4.01, S 9.07. 1H NMR (400 MHz, CDCl3, CH2Cl2). C24H33N3O3S (443.60): calcd. C 64.98, H 7.50, N 9.47, S 7.23;
25 °C): δ = 1.70–1.73 (m, 12 H, CH2+CH3), 3.42–3.45 (m, 4 H, CH2), found C 64.70, H 7.56, N 9.21, S 6.98. 1H NMR (400 MHz, CDCl3,
6.12 (d, J = 4.8 Hz, 1 H, CHth), 7.27 (d, J = 4.8 Hz, 1 H, CHth), 7.38 25 °C): δ = 0.90–0.93 (m, 6 H, CH3), 1.31–1.38 (m, 4 H, CH2), 1.56–
(d, J = 14 Hz, 1 H, CH), 7.58 (t, J = 13.2 Hz, 1 H, CH), 8.00 ppm (d, 1.61 (m, 4 H, CH2), 1.63–1.70 (m, 6 H, CH2), 3.38–3.40 (m, 4 H, CH2),
J = 12.8 Hz, 1 H, CH). 13C NMR (100 MHz, CDCl3, 25 °C): δ = 23.72, 3.88–3.92 (m, 4 H, CH2), 6.08 (d, J = 4.8 Hz, 1 H, CHth), 7.22 (d, J =
25.30, 27.53, 51.72, 100.88, 103.79, 106.92, 117.59, 125.48, 141.61, 4.4 Hz, 1 H, CHth), 7.38 (d, J = 13.6 Hz, 1 H, CH), 7.88 (t, J = 13.2 Hz,
149.09, 157.61, 162.69, 164.97, 168.87 ppm. FTIR (HATR): ν̃ = 2852, 1 H, CH), 8.01 ppm (d, J = 12.8 Hz, 1 H, CH). 13C NMR (125 MHz,
2358, 1673, 1514, 1469, 1410, 1349, 1210, 1138, 1112, 987, 927, CDCl3, 25 °C): δ = 13.87, 13.90, 20.24, 20.35, 23.53, 25.07, 30.32,
758 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C18H21NO4S [M]+ 30.40, 40.99, 41.50, 51.47, 106.25, 106.60, 118.06, 125.73, 140.89,
347.11858; found 347.11969. 148.86, 151.59, 156.63, 162.49, 163.14, 168.19 ppm. FTIR (HATR): ν̃ =
2936, 2850, 1703, 1632, 1553, 1513, 1401, 1359, 1331, 1214, 1133,
Chromophore 5c: The title compound was synthesized from alde-
hyde 9c (222 mg) and Meldrum′s acid (360 mg) by following gen- 1051, 993, 884, 748 cm–1. HR-MALDI-MS (DHB): m/z calcd. for
C24H34N3O3S [M + H]+ 444.23154; found 444.23174.
eral procedure GP3 with CH2Cl2 at 25 °C. Yield: 180 mg (38 %); red-
violet solid; m.p. 199 °C; Rf = 0.75 (SiO2; EtOAc/CH2Cl2, 1:10). Chromophore 6c: The title compound was synthesized from alde-
C23H25NO8S (475.51): calcd. C 58.09, H 5.30, N 2.95, S 5.74; found C hyde 9c (222 mg) and N,N′-dibutylbarbituric acid (600 mg) by fol-
57.02, H 5.04, N 2.72, S 5.91; 1H NMR (400 MHz, CDCl3, 25 °C): δ = lowing general procedure GP3 at 25 °C for 3 h. Yield: 448 mg (67 %);
1.73 (s, 6 H, CH3), 1.75 (s, 8 H, CH2+CH3), 1.84–1.86 (m, 4 H, CH2), dark-red solid; m.p. 127 °C; Rf = 0.3 (SiO2; CH2Cl2). C35H49N5O6S
3.67–3.69 (m, 4 H, CH2), 8.23 (s, 1 H, CH), 8.35 (s, 1 H, CH), 8.41 ppm (667.86): calcd. C 62.94, H 7.40, N 10.49, S 4.80; found C 63.19, H
(s, 1 H, CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 23.66, 25.99, 7.62, N 10.20, S 4.61. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 0.93–
27.60, 27.85, 56.85, 102.19, 104.59, 104.62, 107.03, 116.75, 122.44, 0.99 (m, 12 H, CH3), 1.34–1.43 (m, 8 H, CH2), 1.58–1.62 (m, 8 H, CH2),
147.41, 149.57, 151.53, 160.90, 162.44, 163.99, 179.62 ppm. FTIR 1.76–1.86 (m, 6 H, CH2), 3.66–3.68 (m, 4 H, CH2), 3.91–3.97 (m, 8 H,
(HATR): ν̃ = 2921, 2852, 2364, 1690, 1490, 1356, 1271, 1154, 1020, CH2), 8.26 (s, 1 H, CH), 8.46 (s, 1 H, CH), 8.62 ppm (s, 1 H, CH). 13C
920, 787 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C23H25NO8S [M]+ NMR (125 MHz, CDCl3, 25 °C): δ = 13.93, 13.98, 20.29, 20.32, 20.35,
475.12954; found 475.13067. 20.37, 23.70, 26.09, 30.27, 30.31, 41.31, 41.78, 42.03, 42.35, 56.68,
Chromophore 5d: The title compound was synthesized from di- 106.50, 111.33, 118.06, 122.51, 147.09, 149.40, 151.00, 151.25,
aldehyde 9d (276 mg) and Meldrum′s acid (360 mg) by following 152.37, 160.90, 162.28, 162.79, 162.89, 180.13 ppm. FTIR (HATR): ν̃ =
general procedure GP2. Yield: 460 mg (87 %); black solid; Rf = 0.8 2954, 2870, 1654, 1535, 1389, 1365, 1287, 1149, 1100, 950, 787 cm–1.
(SiO2; EtOAc/CH2Cl2, 1:20). C27H29NO8S (527.59): calcd. C 61.47, H HR-MALDI-MS (DHB): m/z calcd. for C35H50N5O6S [M + H]+
5.54, N 2.65, S 6.08; found C 61.21, H 5.64, N 2.64, S 5.91. 1H NMR 668.34763; found 668.34758.
(400 MHz, CDCl3, 25 °C): δ = 1.73–1.74 (m, 14 H, CH2+CH3), 1.80– Chromophore 6d: The title compound was synthesized from di-
1.85 (m, 4 H, CH2), 3.39–3.42 (m, 4 H, CH2), 7.27 (d, J = 15.6 Hz, 1 aldehyde 9d (276 mg) and N,N′-dibutylbarbituric acid (600 mg) by
H, CH), 7.38 (d, J = 14.8 Hz, 1 H, CH), 7.49 (s, 1 H, CHth), 7.77 (dd, following general procedure GP2. Yield: 634 mg (88 %); black solid;
J1 = 12, J2 = 14.8 Hz, 1 H, CH), 7.93 (dd, J1 = 12, J2 = 14.8 Hz, 1 H, Rf = 0.55 (SiO2; CH2Cl2). C39H53N5O6S (719.94): calcd. C 65.06, H 7.42,
CH), 8.08 ppm (dd, J1 = 12, J2 = 16 Hz, 2 H, CH). 13C NMR (125 MHz, N 9.73, S 4.45; found C 65.15, H 7.54, N 9.69, S 4.38. 1H NMR
CDCl3, 25 °C): δ = 23.68, 25.63, 27.79, 56.11, 104.65, 104.75, 108.20, (400 MHz, CDCl3, 25 °C): δ = 0.94–0.97 (m, 12 H, CH3), 1.32–1.43 (m,
108.39, 122.24, 122.68, 128.69, 135.42, 145.75, 146.45, 157.37, 8 H, CH2), 1.58–1.64 (m, 8 H, CH2), 1.71–1.81 (m, 6 H, CH2), 3.37–
158.49, 161.45, 161.54, 163.60, 163.76, 170.30 ppm. FTIR (HATR): ν̃ = 3.40 (m, 4 H, CH2), 3.90–3.95 (m, 8 H, CH2), 7.27 (d, J = 13.6 Hz, 1
2931, 2358, 1703, 1556, 1453, 1354, 1277, 1141, 1106, 991, 926, H, CH), 7.32–7.39 (m, 1 H, CH), 7.52 (s, 1 H, CHth), 8.06–8.12 (m, 3
787, 715 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C27H29NO8S [M]+ H, CH), 8.22 ppm (dd, J1 = 12.4, J2 = 14.8 Hz, 1 H, CH). 13C NMR
527.16084; found 527.16244. (125 MHz, CDCl3, 25 °C): δ = 13.99, 14.03, 20.37, 20.47, 23.75, 25.68,
30.39, 30.46, 41.53, 41.56, 42.06, 56.12, 112.23, 112.51, 122.80,
122.91, 123.24, 129.26, 134.57, 145.35, 146.26, 151.26, 151.30,
hyde 9a (195 mg) and N,N′-dibutylbarbituric acid (288 mg) by fol-
156.57, 157.56, 162.00, 162.09, 162.55, 162.70, 169.66 ppm. FTIR
lowing general procedure GP3 with CH2Cl2 at 25 °C. Yield: 260 mg
(HATR): ν̃ = 2954, 2864, 2360, 1654, 1558, 1496, 1402, 1370, 1152,
(62 %); orange solid; m.p. 172 °C; Rf = 0.8 (SiO2; CH2Cl2/acetone,
100:5). C22H31N3O3S (417.57): calcd. C 63.28, H 7.48, N 10.06, S 7.68; 1102, 987, 789 cm–1. HR-MALDI-MS (DHB): m/z calcd. for
C39H54N5O6S [M + H]+ 720.37893; found 720.37825.
found C 63.32, H 7.52, N 10.04, S 7.61. 1H NMR (500 MHz, CDCl3,
25 °C): δ = 0.93 (t, J = 7.5 Hz, 6 H, CH3), 1.34–1.38 (m, 4 H, CH2), Chromophore 7a: The title compound was synthesized from alde-
1.60–1.72 (m, 10 H, CH2), 3.56–3.57 (m, 4 H, CH2), 3.91–3.94 (m, 4 hyde 9a (196 mg) and N,N′-dibutyl-2-thiobarbituric acid (308 mg)
H, CH2), 6.31 (d, J = 5 Hz, 1 H, CHth), 7.60 (s, 1 H, CHth), 8.30 ppm by following general procedure GP3 at 25 °C. Yield: 252 mg (58 %);
(s, 1 H, CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 14.09, 20.46, pink-red solid; m.p. 216 °C; Rf = 0.65 (SiO2; CH2Cl2). C22H31N3O2S2
Full Paper
(433.63): calcd. C 60.94, H 7.21, N 9.69, S 14.79; found C 61.21, H Chromophore 8a: The title compound was synthesized from alde-
7.33, N 9.54, S 14.51. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 0.93– hyde 9a (195 mg) and indan-1,3-dione (175 mg) by following gen-
0.96 (m, 6 H, CH3), 1.36–1.42 (m, 4 H, CH2), 1.69–1.75 (m, 10 H, CH2), eral procedure GP3 at 25 °C. Yield: 226 mg (70 %); dark-green-red
3.61–3.62 (m, 4 H, CH2), 4.45–4.50 (m, 4 H, CH2), 6.39 (d, J = 5 Hz, 1 solid; m.p. 182 °C; Rf = 0.6 (SiO2; CH2Cl2/EtOAc, 10:1). C19H17NO2S
H, CHth), 7.63 (d, J = 5 Hz, 1 H, CHth), 8.28 ppm (s, 1 H, CH). 13C (323.41): calcd. C 70.56, H 5.30, N 4.33, S 9.91; found C 70.44, H 5.52,
NMR (125 MHz, CDCl3, 25 °C): δ = 14.10, 14.15, 20.47, 23.73, 25.66, N 4.32, S 9.79. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 1.70–1.72 (m,
29.35, 47.49, 48.36, 51.70, 100.47, 109.59, 123.97, 146.53, 152.83, 6 H, CH2), 3.52–3.54 (m, 4 H, CH2), 6.23 (d, J = 5 Hz, 1 H, CHth),
161.08, 162.49, 175.84, 178.92 ppm. FTIR (HATR): ν̃ = 2919, 2851, 7.59–7.61 (m, 3 H, CHth+CHind), 7.71 (s, 1 H, CH), 7.75–7.77 ppm
1630, 1484, 1412, 1381, 1239, 1151, 1105, 995, 947, 886, 778 cm–1. (m, 2 H, CHind). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 23.69, 25.36,
HR-MALDI-MS (DHB): m/z calcd. for C22H32N3O2S2 [M + H]+ 51.38, 107.59, 114.70, 121.45, 121.75, 133.40, 133.60, 136.55, 140.34,
434.19304; found 434.19302. 141.44, 149.46, 172.78, 190.82, 191.74 ppm. FTIR (HATR): ν̃ = 2922,
2850, 1643, 1561, 1483, 1406, 1376, 1249, 1195, 1103, 1078,
Chromophore 7b: The title compound was synthesized from alde- 746 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C19H18NO2S [M + H]+
hyde 9b (221 mg) and N,N′-dibutyl-2-thiobarbituric acid (307 mg) 324.10528; found 324.10454.
by following general procedure GP2 at 40 °C. Yield: 261 mg (57 %);
dark-green solid; m.p. 175 °C; Rf = 0.4 (SiO2; CH2Cl2). C24H33N3O2S2 Chromophore 8b: The title compound was synthesized from alde-
(459.66): calcd. C 62.71, H 7.24, N 9.14, S 13.95; found C 62.69, H hyde 9b (221 mg) and indan-1,3-dione (175 mg) by following gen-
7.31, N 8.98, S 13.81. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 0.93– eral procedure GP2 at 40 °C for 48 h. Yield: 178 mg (51 %); tawny
0.97 (m, 6 H, CH3), 1.35–1.43 (m, 4 H, CH2), 1.68–1.73 (m, 10 H, CH2), solid; m.p. 204 °C; Rf = 0.7 (SiO2; CH2Cl2/EtOAc, 20:1). C21H19NO2S
3.47–3.48 (m, 4 H, CH2), 4.44–4.48 (m, 4 H, CH2), 6.19 (d, J = 4.8 Hz, (349.45): calcd. C 72.18, H 5.48, N 4.01, S 9.18; found C 72.04, H 5.57,
1 H, CHth), 7.33 (d, J = 4 Hz, 1 H, CHth), 7.46 (d, J = 13.6 Hz, 1 H, N 3.97, S 8.95. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 1.66–1.71 (m,
CH), 7.93 (t, J = 13.2 Hz, 1 H, CH), 8.04 ppm (d, J = 12.8 Hz, 1 H, 6 H, CH2), 3.37–3.39 (m, 4 H, CH2), 6.06 (t, J = 4.5 Hz, 1 H, CHth),
CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 14.09, 14.11, 20.45, 20.51, 7.17 (d, J = 1.5 Hz, 1 H, CHth), 7.33 (dd, J1 = 2, J2 = 14.5 Hz, 1 H,
23.69, 25.37, 29.37, 29.42, 47.71, 48.20, 52.00, 106.27, 108.10, 118.89, CH), 7.51 (dd, J1 = 2.5, J2 = 12.5 Hz, 1 H, CH), 7.62–7.65 (m, 2 H,
126.43, 150.07, 157.26, 161.05, 162.07, 169.99, 178.96 ppm. FTIR CHind), 7.74 (dd, J1 = 3, J2 = 14.5 Hz, 1 H, CH), 7.80–7.82 ppm (m,
(HATR): ν̃ = 2921, 2851, 1633, 1508, 1336, 1206, 1104, 1051, 2 H, CHind). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 23.74, 25.20,
986 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C24H33N3O2S2 [M]+ 51.51, 106.04, 117.32, 121.67, 122.01, 122.30, 126.15, 133.92, 134.11,
459.20087; found 459.20101. 138.98, 140.77, 142.09, 146.04, 146.33, 166.92, 191.37, 191.67 ppm.
FTIR (HATR): ν̃ = 2921, 2852, 1642, 1561, 1517, 1418, 1350, 1210,
Chromophore 7c: The title compound was synthesized from alde- 1101, 1058, 986, 738 cm–1. HR-MALDI-MS (DHB): m/z calcd. for
hyde 9c (222 mg) and N,N′-dibutyl-2-thiobarbituric acid (640 mg) C21H20NO2S [M + H]+ 350.12093; found 350.12039.
by following general procedure GP3 at 25 °C. Yield: 440 mg (63 %); Chromophore 8c: The title compound was synthesized from alde-
dark-brown solid; m.p. 172 °C; Rf = 0.6 (SiO2; CH2Cl2/Hex, 4:1). hyde 9c (222 mg) and indan-1,3-dione (366 mg) by following gen-
C35H49N5O4S3 (699.98): calcd. C 60.05, H 7.06, N 10.00, S 13.74; eral procedure GP3 at 25 °C. Yield: 398 mg (83 %); dark-brown solid;
found C 60.01, H 7.13, N 9.95, S 13.57. 1H NMR (400 MHz, CDCl3, m.p. 243 °C; Rf = 0.6 (SiO2; CH2Cl2/EtOAc, 10:1). C29H21NO4S (479.55):
25 °C): δ = 0.93–0.99 (m, 12 H, CH3), 1.35–1.42 (m, 8 H, CH2), 1.66– calcd. C 72.63, H 4.41, N 2.92, S 6.69; found C 72.56, H 4.49, N 2.91,
1.70 (m, 8 H, CH2), 1.78–1.88 (m, 6 H, CH2), 3.70–3.73 (m, 4 H, CH2), S 6.64. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 1.78–1.80 (m, 2 H, CH2),
4.41–4.46 (m, 8 H, CH2), 8.25 (s, 1 H, CH), 8.44 (s, 1 H, CH), 8.66 ppm 1.87–1.89 (m, 4 H, CH2), 3.69–3.72 (m, 4 H, CH2), 7.68 (s, 1 H, CH),
(s, 1 H, CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 14.02, 14.08, 7.71–7.72 (m, 2 H, CHind), 7.76–7.78 (m, 2 H, CHind), 7.86–7.88 (m, 1
20.37, 20.39, 20.40, 23.70, 26.21, 29.23, 47.70, 48.34, 48.55, 48.80, H, CHind), 7.89–7.93 (m, 3 H, CH+CHind), 7.96–7.98 (m, 1 H, CHind),
56.83, 107.26, 112.00, 118.95, 123.30, 148.18, 150.37, 153.16, 159.18, 9.00 ppm (s, 1 H, CH). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 23.83,
160.59, 161.49, 161.58, 179.11, 179.13, 180.67 ppm. FTIR (HATR): ν̃ = 25.92, 56.80, 118.75, 121.20, 122.56, 122.88, 123.00, 123.17, 123.45,
2927, 2855, 1655, 1529, 1477, 1365, 1281, 1198, 1153, 1118, 948, 123.57, 134.74, 134.97, 134.99, 135.26, 137.74, 140.20, 140.73,
783 cm–1. HR-MALDI-MS (DHB): m/z calcd. for C35H50N5O4S3 [M + 141.80, 142.48, 149.95, 178.48, 189.74, 190.65, 190.66, 191.06 ppm.
H]+ 700.30194; found 700.30096. FTIR (HATR): ν̃ = 3070, 2929, 2850, 1676, 1552, 1486, 1383, 1328,
1279, 1179, 1151, 1102, 944, 878, 727, 676 cm–1. HR-MALDI-MS
Chromophore 7d: The title compound was synthesized from di-
(DHB): m/z calcd. for C29H22NO4S [M + H]+ 480.12641; found
aldehyde 9d (276 mg) and N,N′-dibutyl-2-thiobarbituric acid
480.12666.
(640 mg) by following general procedure GP2 in CH3CN. Yield:
609 mg (81 %); black solid; Rf = 0.8 (SiO2; CH2Cl2). C39H53N5O4S3 Chromophore 8d: The title compound was synthesized from di-
(752.06): calcd. C 62.28, H 7.10, N 9.31, S 12.79; found C 62.34, H aldehyde 9d (256 mg) and indan-1,3-dione (366 mg) by following
7.21, N 9.20, S 12.49. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 0.93– general procedure GP2 in CH3CN. Chromophore 8d is sparingly sol-
0.98 (m, 12 H, CH3), 1.35–1.43 (m, 8 H, CH2), 1.64–1.82 (m, 14 H, uble in chlorinated solvents. Yield: 430 mg (81 %); black gold solid.
CH2), 3.45–3.48 (m, 4 H, CH2), 4.41–4.45 (m, 8 H, CH2), 7.30 (d, J = Rf = 0.75 (SiO2; CH2Cl2/CH3OH, 50:1). C33H25NO4S (531.62): calcd. C
14.8 Hz, 1 H, CH), 7.35–7.41 (m, 1 H, CH), 7.43 (s, 1 H, CHth), 8.01– 73.56, H 4.74, N 2.63, S 6.03; found C 72.97, H 5.00, N 2.41, S 5.64.
1
8.11 (m, 3 H, CH), 8.22 ppm (dd, J1 = 12.4, J2 = 14.4 Hz, 1 H, CH). H NMR (400 MHz, CD2Cl2, 25 °C): δ = 1.71–1.74 (m, 2 H, CH2), 1.81–
13
C NMR (125 MHz, CDCl3, 25 °C): δ = 14.01, 14.03, 20.36, 20.43, 1.87 (m, 4 H, CH2), 3.36–3.39 (m, 4 H, CH2), 7.24 (d, J = 15.2 Hz, 1
23.67, 25.68, 29.26, 29.28, 29.32, 47.90, 47.95, 48.39, 56.16, 112.51, H, CH), 7.37 (d, J = 14.8 Hz, 1 H, CH), 7.50–7.57 (m, 3 H, CH+CHth),
112.80, 122.62, 123.45, 123.73, 128.98, 135.63, 146.24, 147.05, 7.72–7.80 (m, 4 H, CHind), 7.86–7.94 (m, 5 H, CH+CHind), 8.05 ppm
157.65, 158.63, 160.25, 160.34, 161.15, 161.29, 170.64, 179.22, (dd, J1 = 12, J2 = 15.2 Hz, 1 H, CH). 13C NMR (125 MHz, CD2Cl2,
179.25 ppm. FTIR (HATR): ν̃ = 2956, 2860, 1663, 1551, 1468, 1371, 25 °C): δ = 24.13, 26.08, 56.35, 121.43, 122.02, 122.89, 122.99, 123.07,
1294, 1198, 1154, 1123, 1089, 984, 956, 785 cm–1. HR-MALDI-MS 123.44, 126.23, 126.40, 129.85, 133.64, 133.66, 135.13, 135.19,
(DHB): m/z calcd. for C39H54N5O4S3 [M + H]+ 752.33324; found 135.25, 135.36, 141.27, 141.30, 142.59, 142.60, 143.21, 144.04,
752.33270. 144.45, 145.61, 168.73, 190.49, 190.66, 191.08, 191.10 ppm. FTIR
Full Paper
(HATR): ν̃ = 3499, 2917, 2850, 1673, 1563, 1478, 1320, 1235, 1154, Org. Chem. 2011, 24, 274–281; h) A. Wojciechowski, M. M. M. Raposo,
1143, 983, 733 cm–1. HR-MALDI-MS (DHB): m/z calcd. for M. C. R. Castro, W. Kuznik, I. Fuks-Janczarek, M. Pokladko-Kowar, F. Bureš,
C33H26NO4S [M + H]+ 532.15771; found 532.15699. J. Mater. Sci. Mater. Electron. 2014, 25, 1745–1750.
[13] F. Bureš, Chem. Listy 2013, 107, 834–842.
[14] D. Cvejn, E. Michail, I. Polyzos, N. Almonasy, O. Pytela, M. Klikar, T.
Acknowledgments Mikysek, V. Giannetas, M. Fakis, F. Bureš, J. Mater. Chem. C 2015, 3, 7345–
7355.
This research was supported by the Technology Agency of the [15] a) W. Zou, Y. Liu, Q. Jia, Z. Ge, Chin. J. Org. Chem. 2013, 33, 1522–1526;
Czech Republic (TE01020022, Flexprint). M. L. and F. B. are in- b) R. V. Pereira, M. H. Gehlen, Chem. Phys. Lett. 2006, 426, 311–317; c) C.
debted to the Ministry of Education, Youth and Sports of the Coluccini, A. K. Sharma, M. Caricato, A. Sironi, E. Cariati, S. Righetto, E.
Tordin, C. Botta, A. Forni, D. Pasini, Phys. Chem. Chem. Phys. 2013, 15,
Czech Republic (LG 15030).
1666–1674; d) H. Mokbel, F. Dumur, S. Telitel, L. Vidal, P. Xiao, D.-L. Ver-
sace, M.-A. Tehfe, F. Morlet-Savary, B. Graff, J.-P. Fouassier, D. Gigmes, J.
Keywords: Donor–acceptor systems · Chromophores · Toufaily, T. Hamieh, J. Lalevée, Polym. Chem. 2013, 4, 5679–5687; e) M.
Structure–activity relationships · Charge-transfer · Electron- Caricato, C. Coluccini, D. A. Vander Griend, A. Forni, D. Pasini, New J.
Chem. 2013, 37, 2792–2799; f) R. V. Pereira, M. H. Gehlen, J. Phys. Chem.
withdrawing strength
A 2006, 110, 7539–7546.
[16] a) P. Flores, M. C. Rezende, F. Jara, Dyes Pigm. 2004, 62, 277–281; b) S. E.
[1] W. B. Jensen, J. Chem. Educ. 2007, 84, 924. Boiadjiev, D. A. Lightner, Monatsh. Chem. 2008, 139, 503–511; c) L. A.
[2] H. Strittmatter, S. Hildbrand, P. Pollak, Malonic Acid and Derivatives. Ull- Crawford, H. McNab, Collect. Czech. Chem. Commun. 2009, 74, 995–1009;
mann's Encyclopedia of Industrial Chemistry. 2012, 22, p. 157–174. d) S. Wang, S.-H. Kim, Dyes Pigm. 2009, 80, 314–320; e) K. Kowalski, Ł.
[3] a) P. Pollak, G. Romeder, Malonic Acid and Derivatives. Kirk-Othmer Ency- Szczupak, J. Skiba, O. S. Abdel-Rahman, R. F. Winter, R. Czerwieniec, B.
clopedia of Chemical Technology. 2000, p. 1–22. Therrien, Organometallics 2014, 33, 4697–4705.
[4] a) R. Menegatti, “Green Chemistry – Aspects for the Knoevenagel Reac- [17] a) Y. Nagao, T. Sakai, K. Kozawa, T. Urano, Dyes Pigm. 2007, 73, 344–352;
tion”, in Green Chemistry - Environmentally Benign Approaches (Eds.: M. b) M. C. Rezende, P. Campodonico, E. Abuin, J. Kossanyi, Spectrochim.
Kidwai, N. K. Mishra), InTech, Rijeka, 2012, 13–32; b) G. Jones, “The Acta Part A 2001, 57, 1183–1190; c) S.-H. Kim, Y.-S. Kim, D.-H. Lee, Y.-A.
Knoevenagel Condensation” in Organic Reactions (Ed.: S. E. Denmark), Son, Mol. Cryst. Liq. Cryst. 2011, 550, 240–249.
John Wiley & Sons, Hoboken, 2011, p. 204–599; c) A. M. Asiri, S. A. Khan, [18] a) M. A. N. Razvi, A. H. Bakry, S. M. Afzal, S. A. Khan, A. M. Asiri, Mater.
H. M. Basisi, Int. J. Electrochem. Sci. 2015, 10, 6092–6105. Lett. 2015, 144, 131–134; b) S. M. Lee, W. S. Jahng, J. H. Lee, B. K. Rhee,
[5] a) S. R. Forrest, M. E. Thompson, Chem. Rev. 2007, 107, 923–1386; b) R. D. K. H. Park, Chem. Phys. Lett. 2005, 411, 496–500; c) J. Garín, J. Orduna,
Miller, E. A. Chandross, Chem. Rev. 2010, 110, 1–574; c) G. S. He, L.-S. Tan, J. I. Rupérez, R. Alcalá, B. Villacampa, C. Sánchez, N. Martín, J. L. Segura,
Q. Zheng, P. N. Prasad, Chem. Rev. 2008, 108, 1245–1330; d) Y. Ohmori, M. González, Tetrahedron Lett. 1998, 39, 3577–3580; d) R. Andreu, J.
Laser Photonics Rev. 2010, 4, 300–310. Garín, J. Orduna, R. Alcalá, B. Villacampa, Org. Lett. 2003, 5, 3143–3146;
[6] a) J. Kulhánek, F. Bureš, J. Opršal, W. Kuznik, T. Mikysek, A. Růžička, Asian e) B. R. Cho, J. T. Je, S. J. Lee, S. H. Lee, H. S. Kim, S. J. Jeon, O.-K. Song,
J. Org. Chem. 2013, 2, 422–431; b) P. D. Jarowski, Y. Mo, Chem. Eur. J. C. H. Wang, J. Chem. Soc. Perkin Trans. 2 1996, 2141–2144; f) X. Zhou, A.-
2014, 20, 17214–17221; c) H. Meier, Angew. Chem. Int. Ed. 2005, 44, M. Ren, J.-K. Feng, X.-J. Liu, C.-C. Shu, Chin. J. Chem. 2004, 22, 38–46.
2482–2506; Angew. Chem. 2005, 117, 2536; d) J. Y. Lee, K. S. Kim, B. J. [19] M. El-Sayed, S. Spange, J. Phys. Org. Chem. 2007, 20, 264–270.
Mhin, J. Chem. Phys. 2001, 115, 9484–9489; e) F. Bureš, O. Pytela, M. [20] a) K. Zhou, H. Fu, L. Feng, M. Cui, J. Dai, B. Liu, Chem. Commun. 2015,
Kivala, F. Diederich, J. Phys. Org. Chem. 2011, 24, 274–281. 51, 11665–11668; b) H. Lee, M. Y. Berezin, K. Guo, J. Kao, S. Achilefu, Org.
[7] F. Bureš, RSC Adv. 2014, 4, 58826–58851. Lett. 2009, 11, 29–32.
[8] a) H. S. Nalwa, Adv. Mater. 1993, 5, 341–358; b) T. Verbiest, S. Houbrechts, [21] F. Wu, L. Zhu, S. Zhao, Q. Song, C. Yang, Dyes Pigm. 2016, 124, 93–100.
M. Kauranen, K. Clays, A. Persoons, J. Mater. Chem. 1997, 7, 2175–2189; [22] a) S. Yagai, J. Photochem. Photobiol. C 2006, 7, 164–182; b) R. B. K. Siram,
c) D. F. Eaton, Science 1991, 253, 281–287; d) L. R. Dalton, P. A. Sullivan, K. Tandy, M. Horecha, P. Formanek, M. Stamm, S. Gevorgyan, F. C. Krebs,
D. H. Bale, Chem. Rev. 2010, 110, 25–55. A. Kiriy, P. Meredith, P. L. Burn, E. B. Namdas, S. Patil, J. Phys. Chem. C
[9] a) P. Batail, Chem. Rev. 2004, 104, 4887–4890; b) S. Allard, M. Forster, B. 2011, 115, 14369–14376; c) R. Schmidt, M. Stolte, M. Grüne, F. Würthner,
Souharce, H. Thiem, U. Scherf, Angew. Chem. Int. Ed. 2008, 47, 4070– Macromolecules 2011, 44, 3766–3776.
4098; Angew. Chem. 2008, 120, 4138. [23] M. Klikar, F. Bureš, O. Pytela, T. Mikysek, Z. Padělková, A. Barsella, K. Dork-
[10] a) K. Hara, T. Sato, R. Katoh, A. Furube, Y. Ohga, A. Shinpo, J. Phys. Chem. enoo, S. Achelle, New J. Chem. 2013, 37, 4230–4240.
B 2003, 107, 597–606; b) K. Hara, T. Sato, R. Katoh, A. Furube, T. Yoshihara, [24] M. Klikar, I. V. Kityk, D. Kulwas, T. Mikysek, O. Pytela, F. Bureš, New J.
M. Murai, M. Kurashige, S. Ito, A. Shinpo, S. Suga, H. Arakawa, Adv. Funct. Chem. 2017, 41, 1459–1472.
Mater. 2005, 15, 246–252; c) L. Giribabu, M. Chandrasekheram, M. L. [25] R. Nazir, B. Thorsted, E. Balčiunas, L. Mazur, I. Deperasińska, M. Samoć, J.
Kantham, V. G. Reddy, D. Satyanarayana, O. S. Rao, P. Y. Reddy, Indian J. Brewer, M. Farsari, D. T. Gryko, J. Mater. Chem. C 2016, 4, 167–177.
Chem. Sect A 2006, 45, 629–634; d) G. Li, K.-J. Jiang, Y.-F. Li, S.-L. Li, L.-M. [26] a) P. Solanke, F. Bureš, O. Pytela, J. Kulhánek, Z. Padělková, Synthesis 2013,
Yang, J. Phys. Chem. C 2008, 112, 11591–11599; e) K. Srinivas, K. Yesudas,
45, 3044–3051; b) P. Solanke, F. Bureš, O. Pytela, M. Klikar, T. Mikysek, L.
K. Bhanuprakash, V. J. Rao, L. Giribabu, J. Phys. Chem. C 2009, 113, 20117–
Mager, A. Barsella, Z. Růžičková, Eur. J. Org. Chem. 2015, 5339–5349.
20126; f) K. S. V. Gupta, J. Zhang, G. Marotta, M. A. Reddy, S. P. Singh, A.
[27] H. Hartmann, S. Scheithauer, J. Prakt. Chem. 1969, 311, 827–843.
Islam, L. Han, F. De Angelis, M. Chandrasekharam, M. Pastore, Dyes Pigm.
[28] M. Blanchard-Desce, V. Alain, P. V. Bedworth, S. R. Marder, A. Fort, C.
2015, 113, 536–545; g) G. S. Reddy, S. Ramkumar, A. M. Asiri, S. Anandan,
Runser, M. Barzoukas, S. Lebus, R. Wortmann, Chem. Eur. J. 1997, 3, 1091–
Spectrochim. Acta Part A 2015, 145, 531–539; h) Y. Wu, W. Zhu, Chem.
1104.
Soc. Rev. 2013, 42, 2039–2058.
[11] F. Freeman, Chem. Rev. 1969, 69, 591–624. [29] a) I. M. Downie, E. J. Martyn, H. Heaney, K. F. Shuaibar, Tetrahedron 1993,
[12] a) M. Kivala, F. Diederich, Acc. Chem. Res. 2009, 42, 235–248; b) F. Bureš, 49, 4015–4034; b) J. A. Clarke, O. Meth-Cohn, Tetrahedron Lett. 1975, 16,
W. B. Schweizer, J. C. May, C. Boudon, J.-P. Gisselbrecht, M. Gross, I. Bi- 4705–4708.
aggio, F. Diederich, Chem. Eur. J. 2007, 13, 5378–5387; c) J. C. May, I. [30] F. Texier-Boullet, A. Foucaud, Tetrahedron Lett. 1982, 23, 4927–4928.
Biaggio, F. Bureš, F. Diederich, Appl. Phys. Lett. 2007, 90, 251106; d) F. [31] a) C. W. Bird, Tetrahedron 1986, 42, 89–92; b) C. W. Bird, Tetrahedron
Bureš, O. Pytela, F. Diederich, J. Phys. Org. Chem. 2009, 22, 155–162; e) F. 1985, 41, 1409–1414; c) S. I. Kotelevskii, O. V. Prezhdo, Tetrahedron 2001,
Bureš, W. B. Schweizer, C. Boudon, J.-P. Gisselbrecht, M. Gross, F. Diede- 57, 5715–5729; d) T. M. Krygowski, H. Szatylowicz, O. A. Stasyuk, J. Dom-
rich, Eur. J. Org. Chem. 2008, 994–1004; f) Y.-L. Wu, F. Bureš, P. D. Jarowski, inikowska, M. Palusiak, Chem. Rev. 2014, 114, 6383–6422.
W. B. Schweizer, C. Boudon, J.-P. Gisselbrecht, F. Diederich, Chem. Eur. J. [32] A. A. Isse, A. Gennaro, J. Phys. Chem. B 2010, 114, 7894–7899.
2010, 16, 9592–9605; g) F. Bureš, O. Pytela, M. Kivala, F. Diederich, J. Phys. [33] OPChem, O. Pytela, version 8.1, webpage: http://bures.upce.cz/OPgm.
Full Paper
[34] a) D. Cvejn, E. Michail, K. Seintis, M. Klikar, O. Pytela, T. Mikysek, N. Almo- H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. Bear-
nasy, M. Ludwig, V. Giannetas, M. Fakis, F. Bureš, RSC Adv. 2016, 6, 12819– park, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J.
12828; b) L. Yan, X. Chen, Q. He, Y. Wang, X. Wang, Q. Guo, F. Bai, A. Xia, Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,
J. Phys. Chem. A 2012, 116, 8693–8705; c) F. Terenziani, C. Le Drouma- M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken,
guet, C. Katan, O. Mongin, M. Blanchard-Desce, ChemPhysChem 2007, 8, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.
723–734. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma,
[35] Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich,
Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Men- A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox,
nucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Gaussian, Inc., Wallingford CT, 2013.
Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, Received: January 18, 2017

Malonic Acid Derivatives On Duty As Electron-Withdrawing Units in Push-Pull Molecules

Uploaded by

Copyright:

Available Formats

Malonic Acid Derivatives On Duty As Electron-Withdrawing Units in Push-Pull Molecules

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Malonic Acid Derivatives On Duty As Electron-Withdrawing Units in Push-Pull Molecules

Uploaded by

Copyright:

Available Formats

DOI: 10.1002/ejoc.

201700070 Full Paper

Introduction Organic push–pull chromophores currently constitute an in-

Scheme 1. Synthesis of N,N′-dibutyl(thio)barbituric acids DBB and DBTB.

Scheme 2. Construction of PIT aldehydes 9a–d.

Scheme 3. General synthetic pathway to chromophores 1–8 through Knoevenagel condensation.

X-ray Analysis by slow diffusion of hexane into the corresponding dichloro-

The longest wavelength absorption maxima of chromophores

Figure 4. Energy level diagram of averaged values of the electrochemical

more negative values upon both extension of the π-system and

One Photon Absorption

Table 2. DFT calculated parameters of chromophores 1–8.

You might also like