Journal of Organometallic Chemistry 636 (2001) 164– 171

www.elsevier.com/locate/jorganchem

UV and Raman study of thermochromic phase transition in

poly(di-n-hexylgermane)
Sergey S. Bukalov a, Larissa A. Leites a, Irina V. Krylova b, Mikhail P. Egorov b,*
a
A.N. Nesmeyano6 Institute of Organoelement Compounds, Scientific and Technical Center on Raman Spectroscopy, Russian Academy of Sciences,
28 Va6ilo6a Street, 119991 Moscow, Russia
b
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 117913 Moscow, Russia

Received 23 April 2001; accepted 27 June 2001

Dedicated to Professor Dr Oleg Nefedov on the occasion of his 70th birthday

Abstract

The thermochromic phase transition of poly(di-n-hexylgermane) (1) was reinvestgated using low-molecular-weight (lmw) and
high-molecular-weight (hmw) polymer samples. The equilibrium phase transition temperature Tc of 1, determined by variable
temperature Raman and UV spectroscopy as well as by DSC, was found to lie not in the interval from +15 to − 10°C, as was
reported previously, but in the region 45–55 °C, that is, very close to Tc of the Si and Sn analogues. Thus, the phase behaviour
of the polymetallanes [nHex2M]n, M=Si, Ge, Sn is governed not by the nature of the main chain but by intermolecular
interactions of the substituent groups. The nature of the order– disorder phase transition of 1 depends on the polymer molecular
weight and the sample thermal history. Above Tc, hmw polymer 1 exists as hexagonal columnar mesophase while lmw 1 is in
amorphous state, both with disordered backbone. On cooling to room temperature, hmw polymer transforms to a crystalline
modification with an all-anti conformation of the backbone and ordered hexyl groups, whereas the process of ordering of the main
chain for lmw sample is more complicated. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Polygermane; Phase transition; Raman; UV; DSC

1. Introduction molar absorptivity were found to increase regularly

with increasing chain length, in a manner typical for
Chemistry and physical chemistry of polydiorganyl- p-conjugated systems. In 1966 Shorygin, Nefedov et al.
metallanes, whose macromolecules contain catenated [4] published analogous UV data for linear ho-
homoatomic chains of Group 14 elements — silicon, moatomic chains consisting of SiR2, GeR2 and SnR2
germanium, and tin, are rapidly and dynamically devel- units. They also observed a remarkable red shift of the
oping areas of modern organometallic chemistry. In lowest-energy absorption band with the chain lengthen-
this paper, it is pertinent to emphasise a fundamental ing, the transition energy for a given chain length
contribution to this field made by pioneering papers of decreasing in the order Si, Ge, Sn. Moreover, these
Nefedov and his co-workers in the early 1960s on the authors made an important suggestion that there is no
synthesis and properties of polysilanes and first principal difference between interaction of s-bonds in
polygermanes [1,2]. these chain compounds and of p-bonds in linear conju-
In 1964, Gilman et al. [3] reported the family of gated polyenes, the degree of interaction between the
permethylated straight-chain polysilanes Me(SiMe2)n - chain units just increasing in the series
Me with n = 2–8 along with their UV spectra. Surpris-
ingly, the position of the absorption band, umax, and the CR2 B SiR2 B GeR2 B SnR2 B CHCH

* Corresponding author. Tel.: + 7-095-135-5309; fax: +7-095-135-

These first findings, along with some others published
5308. later (see, e.g. [5,6]), laid the foundation for the concept
E-mail address: [email protected] (M.P. Egorov). of s–s conjugation, first reviewed by Pitt [7]. Corre-

0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01096-8
 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171 165

sponding theoretical bases can be found in the Dewar’s data obtained for the latter polymer have demonstrated
comprehensive paper [8]. The ‘s-delocalization’ is now that it undergoes a thermochromic PT at Tc ca. 50 °C,
commonly viewed as an intrinsic property of catenated that is, at the temperature close to that for the silicon
chains of s-bonded Group 14 heavy atoms [9]. More- congener. At the same time, an analogous PT of
over, Adams and Dräger [10] came up with an idea that poly(di-n-hexylgermane) (1), which was synthesized and
the red shift of the UV absorption band with increasing investigated by Miller et al. [13], was reported [13b] to
chain length observed for oligomeric polystannanes take place on cooling, between + 15 and −10°C,
could be interpreted as the onset of formation of a though the nature of this PT appeared absolutely the
metal-like electronic band. On this basis they proposed same as for the corresponding polysilane [13b,14]. Such
for such compounds the term ‘molecular metals’. an irregular behaviour of Tc for the polymers [nHex2M]n
Later high-molecular-weight s – s conjugated polydi- in the series M= Si, Ge, Sn seems unlikely.
alkylmetallanes [R2M]n M =Si, Ge, Sn, became avail- Later 1 was synthesized and studied also by Mochida
able [11–16]. Electronic structure of these polymers of a et al. [15]. It is notable that the room-temperature UV
novel type is discussed in the reviews [11], as well as in data reported for 1 by the two groups of investigators
Refs. [17a,18]. Delocalization of s electrons along the (Refs. [13,15]) are different. The solid hmw (Mw =
chain of M atoms results in unique optoelectronic and 950000) sample [13b] exhibited a broad UV band at 332
electrophysical properties of polymetallanes, which are nm, which was assigned to hexagonal columnar
therefore of great interest as potential photodiodes, mesophase (hcm) on the basis of the WAXD data [14].
photoresists, low band-gap one-dimensional semicon- The lmw (Mw = 9000) polymer film reported in [15]
ductors, and materials for non-linear optics [17]. exhibited a complicated contour consisting of two over-
Polymetallanes can exist in amorphous, mesomorphic lapping UV bands: a broad one with umax at 317 and a
and crystalline states, whereas the chain of M atoms narrow one with umax at 339 nm, which were assigned
can adopt different conformations. The chain can be as helical (all-D) and trans (all-A) conformations of the
disordered and can also form helices with a set of Ge backbone, respectively. Thus, neither the UV data,
dihedral angles in the M– M – M – M fragment, the nor their interpretations given by the two groups agree.
extreme case of a helix with =180° being a planar The difference in the UV patterns reported could be
zigzag structure. The latter was designated all-trans due to the difference in the polymer molecular weights,
until recently, when a new nomenclature for linear as it was observed for polysilanes (see, e.g. [22]).
chain conformations has been proposed and new sym- With this in mind, we decided to reinvestigate the PT
bols are recommended [11a,11b,19]. For instance, the of two sets of samples of [nHex2Ge]n, those with lmw
term all-anti (all-A) is now used instead of all-trans, 7/3 and hmw, by variable temperature UV–vis and Raman
helical conformation with =154° is named all-de6iant spectroscopy and by DSC. Our aim was to check the
(all-D) and also chain units with = 165° (transoid, T) PT temperature and to clarify the effect of molecular
are considered among others. weight. Besides, comparison of the data obtained for
According to quantum chemistry calculations, the three polymers [nHex2M]n in the series M= Si, Ge, Sn
degree of s–s conjugation depends on the chain con- will allow us to elucidate the effect of the element M
formation, the all-A structure favouring to maximum and of the substituents on the phase behaviour of these
interaction of the s-orbitals of the adjacent M–M polymetallanes.
bonds (see reviews [11] and references therein). Confor-
mational transformations of polymetallane chains show
themselves as spectacular phase transitions (PTs) of the 2. Results and discussion
first order and of order– disorder type; they are accom-
panied by substantial changes in optical and electro- 2.1. UV and DSC data
physical polymer properties [11,13b,16b,20,21].
Thermochromic PTs have been widely studied on Freshly prepared films of the hmw polymer samples
examples of numerous polysilanes [11]. The most inves- exhibit at room temperature different UV patterns,
tigated is poly(di-n-hexylsilane) whose PT with equi- depending on the conditions of the film preparation. If
librium PT temperature Tc in the interval 40– 50 °C has the films are obtained from a diluted solution in hex-
been thoroughly explored by the whole armamentarium ane, then the temperature evolution of the UV spec-
of physical methods. It is of fundamental interest to trum, reflecting the thermochromic phase transition
compare the behaviour of analogous polymers (Fig. 1), is quite similar to that reported by Miller et al.
[nHex2M]n in the series M= Si, Ge and Sn. Recently the [13]: a broad band at ca. 335 nm (with a half-width
first representatives of high-molecular-weight poly(di-n- Dw1/2 of about 3500–4000 cm − 1) is gradually replaced
alkylstannanes) were synthesized and studied [16], in- by a sharp band at ca. 380 nm (Dw1/2 about 1500
cluding poly(di-n-hexylstannane). Variable temperature cm − 1). According to [14], the former band corresponds
UV –vis [16b] and Raman [20] as well as DSC [16b] to hcm, while the latter to a crystalline phase with an
166 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171

nm (Dw1/2 about 2500 cm − 1), present in various ratios.

The latter band was mentioned in [13b] as an intermedi-
ate, it disappeared after thermal treatment. Actually, in
our experiments the band at ca. 350 nm, if present,
disappears on heating first, before that at ca. 380 nm,
and only the band at ca. 335 nm persists above Tc.
The PT of the lmw samples also takes place on
heating to ca. 50 °C, but the overall UV pattern,
reflecting this PT, differs from that of the hmw samples.
At room temperature, the UV spectra of freshly pre-
pared films of the lmw polymer show themselves as
complicated absorptions of various shapes, in which the
curve-fitting analysis reveals the same three bands (at
Fig. 1. Temperature evolution of the UV spectrum of the hmw sample ca. 335, ca. 350 and ca.380 nm), which were observed
of [nHex2Ge]n (prepared as a thin film cast from a diluted solution in for hmw samples, but in different proportions. How-
hexane), reflecting its thermochromic phase transition with participa- ever, when the lmw samples are heated to 50 °C and
tion of bands II and IV. above, all these bands disappear and only a very broad
band with umax at ca. 320 nm (Dw1/2 about 5000 cm − 1)
all-trans (all-A) backbone conformation. However, is observed. When the lmw film is gradually cooled
there is a striking difference between our results and from Tc to room temperature (an example of such PT
those reported in Ref. [13]: we have observed this PT process is given in Fig. 3), the initial UV spectrum does
not on cooling but on heating to ca. 50 °C. Thus, the not restore, but a complicated pattern is formed with
process described above and shown in Fig. 1 takes the band at ca. 350 nm predominant.
place when the sample heated to 55 °C is then cooled Thus, equilibrium PT temperatures Tc for both hmw
to room temperature. and lmw samples of 1 were found to be close in value,
The films of hmw 1, prepared under other conditions, lying at about 50 °C (more precisely, in the tempera-
could exhibit in the UV spectrum at room temperature ture interval from 45 to 55 °C). This was confirmed by
complicated contours, like that given in Fig. 2, which DSC data (Fig. 4). Thus, there is a big difference in the
are, according to computer curve-fitting analysis, the Tc values between that reported in Ref. [13] and our
results of an overlap of the above mentioned bands at data [23]. The low Tc value reported in [13] seems to be
ca. 380 and ca. 335 nm, and also of a band at ca. 350 erroneous and could be explained by the presence of
impurities, which always result in a decrease in PT
temperatures.
Numerous variable-temperature UV experiments
have shown that the UV pattern observed at a given
temperature below Tc for both hmw and lmw polymer
samples of 1 is not a single-valued function of tempera-
ture, but strongly depends on the method of the sample

Fig. 2. A room temperature UV spectrum of another thin film of the

hmw sample (prepared under different conditions) with a distinct
band III at ca. 350 nm (a) and the results of the curve-fitting analysis Fig. 3. Temperature evolution on cooling of the UV spectrum of a
after base line subtraction (b). thin film of the lmw sample heated to 50 °C.
 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171 167

Table 1
Absorption bands observed in the UV spectra of poly(di-n-hexylger-
mane) and their assignment

Band I Band II Bands III Band IV

umax (nm) 316–320 332–337 345–355 372–385

Dw1/2 (cm−1) 4500–5500 3200–4000 1500–2500 1000–1500
Phase state Amorphous hcm Cryst. Cryst.
Backbone Disordered Disordered all-A or all-A
conformation all-T

Fig. 4. DSC trace for the lmw sample of [nHex2Ge]n reflecting a Comparison of the results given above with those
first-order phase transition. obtained for various polydialkylsilanes [11,24] and with
preparation, its thermal history and the rate of cooling. the WAXD data for the hmw 1 [14] allows one to assign
Detailed computer analysis has shown that all compli- the four UV bands observed to particular polymer
cated patterns can be represented as superpositions of modifications. Band II at 335 nm corresponds to hcm
the four main bands, having different umax and Dw1/2 [14] (like the band at ca. 315 nm for polysilanes). Band
values (Fig. 5, Table 1), present in variable proportions. I at ca. 320 nm, blue-shifted and more wide compared
Let us designate the observed UV bands and corre- to II, could be assigned to an amorphous phase of the
sponding modifications of 1 by the figures I (umax ca. polymer with a most disordered backbone (its analogue
320 nm), II (umax ca. 335 nm), III (umax ca. 350 nm) and in the spectra of polysilanes is the band at ca. 300 nm).
IV (umax ca. 380 nm). It is necessary to emphasise that The most red-shifted narrow band IV at ca. 380 nm
the exact umax and Dw1/2 values of each UV band evidently corresponds to a crystalline all-A modification
slightly depend on the way of the sample preparation [14]. Basing on the Raman spectra (see below), we
and exhibit slight but regular temperature dependence assign the band III also to an ordered all-A modifica-
which is clearly seen in Fig. 1 for the band IV. The tion, but with a less perfect higher-order structure. As it
same dependence was observed by us for the UV bands is seen from the Table 1, the UV bands of disordered
of the polysilanes studied previously [24]. modifications of the polygermane 1 are red-shifted

Fig. 5. A UV spectrum observed at room temperature for one of the lmw samples (a) and the results of the computer curve-fitting analysis after
base line subtraction (b).
168 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171

compared to those of the corresponding polysilane by [24c,25]. The reason for their different umax values is not
 20 nm, while those of all-A modifications are not. yet clear. We believe that this phenomenon for both
Thus, our UV results for 1 comprise the bands polysilanes and polygermanes could be related to the
reported in Refs. [13,15] and contain additional infor- polymer morphology, to peculiarities of the process of
mation, showing that the nature of the thermochromic polymer crystallization, which depends on film prepara-
PT of 1 depends on the molecular weight of the given tion conditions. As a result, crystalline regions with
polymer sample, though all the samples have close Tc different higher-order structure could be formed; the
values. Above Tc, the hmw samples exist as hcm, latter affects the length of effective anti-sequencies in
whereas the lmw samples are amorphous. The process the main chain, thus determining the degree of s–s
of PT of the hmw samples always involves hcm and the conjugation and consequently the position of the UV
most ordered all-A modification (UV band IV) and band. The same point of view is reciprocated by Ky-
sometimes also a less perfect all-A modification (UV otani et al. [25]. Another possible explanation proposed
band III), whereas in the PT of the lmw samples all the by Michl and West is that only one modification of the
four modifications participate.
polymer is truly all-A, the other forms have small
irregular transoid deviations from it [11b].
2.2. Raman data
Band assignment in the Raman spectrum of 1 can be
made on the basis of the published data on vibrational
The Raman spectra of hmw 1 (at 25, 13 and
spectra of organogermanium compounds [13b,26–30].
− 50 °C) in the region 50– 1600 cm − 1 excited by 488.0
nm line were reported in [13b] together with the FT-Ra- The position of the stretching vibrations of the Ge–C
man spectra in the region 500– 1700 cm − 1. We have bonds (wGe –C) in the Raman spectra of alkylgermanes
studied variable-temperature Raman spectra in the in- and the dependence of w sGe –C on the nature of sub-
terval from 19 to 100 °C for many samples, both hmw stituents were studied in [27,28]. Reliable information
and lmw (as polymer chunks and thin films cast from about the stretching vibration of the Ge–Ge bond
solutions in hexane), using an excitation line of 514.5 (wGe –Ge) was presented by Fontal and Spiro [30] for
nm. The main result is that the room-temperature Me3Ge –GeMe3. Its intense Raman line at 273 cm − 1
Raman spectra of all our hmw and lmw samples are was assigned to wGe –Ge on the basis of normal coordi-
absolutely identical (see Fig. 6a) and closely resemble nate analysis, which showed, however, that this normal
the Raman spectrum reported by Miller et al. [13b] but mode is not fully localized, the wGe –Ge coordinate
obtained at −50 °C. Narrow intense lines, dominating being coupled with the lCGeC deformation, but not
in these spectra, are typical for ordered crystalline with wGe –C. Using these data, the strong narrow lines
polymers and evidently correspond to the modification in the region 200–300 cm − 1 in the Raman spectrum of
having the most s–s conjugated all-A conformation of 1 can be assigned to wGe –Ge, whereas those in the
the Ge backbone [14]. On heating to Tc, the intensity of region 580–650 cm − 1 to wGe –C. Above 700 cm − 1, the
the strong lines, characteristic of the all-A modification, lines corresponding to internal vibrations of nHex
is gradually decreasing (Fig. 6b,c). At ca. 50 °C the groups are situated.
Raman spectrum changes dramatically, confirming the To elucidate the conformational state of the nHex
PT at this point, and exhibits weak broad bands, tails in 1, it was useful to study the Raman spectrum of
typical for the modifications with a disordered polymer a model compound— a monomer nHex2GeBr2
backbone (Fig. 6d–f). (analogous approach was applied by us to the polymer
The most modern highly sensitive Raman spectrome- [nHex2Si]n [24c,31]). The masses of Br and Ge atoms are
ter T64000 used in our experiments permits registration of the same order of magnitude, so that the monomer is
of the Raman spectra of the same thin polymer films as kinematically modelling to some extent the unit of the
were used for obtaining the UV spectra, thus allowing polymer 1.
the strict comparison of the UV and Raman data. The
identity of the room temperature Raman spectra of two
films, one of the hmw polymer (exhibiting the UV band
IV) and the second of the lmw polymer (with the band
III predominant in the UV spectrum) is a strong evi- At room temperature, di(n-hexyl)dibromogermane is
dence that the UV band III also corresponds to an a liquid which should be an equilibrium mixture of
ordered modification with an all-A conformation of the various conformers due to hindered internal rotation
polymer main chain. Analogous phenomenon was ob- about the Ge–C and C–C bonds. Thus, its spectrum in
served for poly(di-n-hexylsilane), whose crystalline all- the region of internal vibrations of nHex groups (800–
A modifications can exhibit in the UV spectra the 1500 cm − 1) should be complicated. This is evident
narrow bands with umax either ca. 375, or ca. 365, or ca. from Fig. 7a. A similar spectrum in this region is
350 nm, or various superpositions of these bands exhibited by all samples of 1 above Tc, pointing to a
 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171 169

disordered state of nHex groups (Fig. 7b). Below Tc, the 2.3. Conclusions
spectrum of 1 in this region becomes much simpler
(Fig. 7c). It is especially notable that for the liquid The thermochromic phase transition of the hmw as
n
Hex2GeBr2 and for the polymer 1 above Tc two fea- well as lmw samples of the polymer [nHex2Ge]n takes
tures in the region 1060– 1080 cm − 1 are observed. The place on heating to ca. 50°C, at nearly the same temper-
band at 1075 cm − 1 is usually associated with the ature as for its Si and Sn congeners. This means that
gauche units in the aliphatic chain, while the neighbour- this phenomenon is governed not by the nature of
ing band at 1060 cm − 1 is characteristic of the trans polymetallane chain but by intermolecular interactions
units [13b,31]. Only the band at 1060 cm − 1 persists in of the side n-hexyl groups.
the spectrum of 1 below Tc. These facts point to nHex [nHex2Ge]n undergoes a complicated phase transition
groups ordering during the phase transition. of order–disorder type with possible participation of

Fig. 6. Temperature evolution on heating of the Raman spectrum of [nHex2Ge]n common to all the samples studied. (a) 20 °C; (b) 35 °C; (c)
48 °C; (d) 50 °C; (e) 80 °C; (f) 100 °C.
170 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171

The Raman spectra were registered using laser Ra-

man spectrometers Jobin-Yvon U-1000 and T64000
with excitation by 514.5 nm line of an Ar+ laser
Spectra Physics 2020. A prism monochromator and
interference filters were applied for filtering laser lines.
Both photomultiplier and CCD detectors were used for
spectra registration. The samples for Raman investiga-
tions were either small polymer chunks sealed in glass
capillaries in vacuo, or just the same polymer films as
used for the UV measurements. To avoid sample de-
struction in the laser beam, the latter was defocused
and minimum light density was applied (exciting laser
power less than 10 mW).
The films of 1, which were studied by the UV and
Raman methods, were free of oxidative destruction
products because their IR spectra contained no broad
IR band in the region 800 cm − 1, corresponding to
w asGeOGe (to identify the latter mode, the IR spectrum
of the cyclic [nHex2GeO]3 was obtained).
The IR spectra of the polymer 1 films and of
[nHex2GeO]3 were registered, using a computerized M-
82 Carl Zeiss spectrophotometer.
For variable-temperature measurements, various
cryostats and heated cells were used. Temperatures
were generally maintained to within 91 °C.
All reactions were carried out under dry Ar atmo-
sphere. Solvents (toluene, hexane, i-PrOH) were dried
and distilled before use by standard methods.
n
Fig. 7. Comparison of the Raman spectra in the region of internal Hex2GeBr2, poly(di-n-hexylgermane) (1) and
vibrations of n-hexyl groups. (a) Liquid nHex2GeBr2; (b) [nHex2Ge]n n
[ Hex2GeO]3 were obtained as described in Ref. [13a].
above Tc (at 80 °C); (c) [nHex2Ge]n below Tc (at 20 °C).
The polymers with lmw and hmw were isolated from
different reactions. In the reaction, leading to lmw
sample, a simple propel stirrer, while in the reaction
several polymer modifications, which differ in inter- leading to hmw polymer a wire stirrer were used.
molecular ordering and in main chain and side chain GPC data for lmw polymer: Mw 73940, Mn 24180,
conformations. Particular characteristics of a given polydispersity 3.05; for hmw polymer: Mw 259660, Mn
phase transition depend on the molecular weight of the 211190, polydispersity 1.22.
sample, its prehistory, and the rate of heating or 1
H-NMR (l, ppm): 0.85 (t), 1.25 (m); 13C-NMR (l,
cooling. ppm): 14.24 (CH3), 17.61, 23.03, 28.76, 31.95, 34.39. 1H
and 13C-NMR spectra were identical for lmw and hmw
polymers. Anal. Calc. for C12H26Ge: C 59.12, H
3. Experimental 10.79, Ge 29.88; Found (for lmw): C 59.50, H 10.85, Ge
29.67.
GPC was performed on a Bruker LC 21 chro-
matograph, using toluene as an eluent at the rate 1
ml/min. Molecular weights are presented relative to Acknowledgements
polystyrene standards.
1
H- and 13C-NMR spectra were recorded on a The authors are indebted to Professor K. Mochida
Bruker AC-200 instrument in CDCl3. for giving his sample of [nHex2Ge]n, to Dr I.I. Dubovik
The UV –vis studies were carried out using a comput- for collecting the DSC data, to M.V. Teplitsky for his
erized M-40 Carl Zeiss spectrophotometer. The samples help in computer curve-fitting analysis of the UV re-
were thin polymer films cast from solutions in hexane. sults, and to JobinYvon company for technical support.
The details of the procedure of sample preparation The authors also acknowledge partial financial support
(temperature, concentration, the rate of solvent evapo- from the Russian Foundation for Basic Research (pro-
ration) were found to strongly influence the initial UV ject nos. 01-03-33057 and 99-03-32885) and INTAS
pattern observed. (grant no. 97-30344).
 S.S. Bukalo6 et al. / Journal of Organometallic Chemistry 636 (2001) 164–171 171

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