J. CHEM. SOC. FARADAY TRANS.

, 1994, 90(2), 327-332 327

Structural Studies on Paracyanogen and Paraisocyanogen

Leonardus W. Jenneskens," Jan W. G. Mahyt and Edward J. Vlietstra
Debye Institute, Department of Physical Organic Chemistry, Utrecht University, Padualaan 8 ,
3584 CH Utrecht, The Netherlands
Simon J. Goede and Friedrich Bickelhaupt
Scheikundig Laboratorium, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam,
The Netherlands

Polymers derived from the isomeric C,N, monomers cyanogen (NCCN) and isocyanogen (CNCN) are investi-
gated. Although both paracyanogen [poly(NCCN)] and paraisocyanogen [poly(CNCN)] consist of carbon and
nitrogen in a close to 1 : 1 ratio, thermogravimetric (TG) and spectroscopic analyses (DRIFT, EPR, UV-VIS-NIR
and XPS) reveal that their molecular structures are markedly different. Despite the occurrence of n-conjugation,
no regular ladder structures are found. In line with the spectroscopic data, conductivity measurements show that
pristine poly(CNCN) and poly(NCCN) are an insulator and a semiconductor, respectively.

The theoretical prediction (extended Huckel bandstructure
calculations) by Whangbo et ul.,' which was corroborated by
valence effective Hamiltonian (VEH) bandstructure calcu-
latioIw2 that paracyanogen [poly(NCCN)] with the regular
ladder structures shown in Scheme 1 possesses metallic
behaviour, has initiated a quest for this potentially intrinsic
organic metal. However, despite the fact that poly(NCCN)
was already prepared in 1815 by Gay Lussac by heat treat-
ment of mercury(r1) cyanide, its intractable nature hampered
its structural el~cidation.~ Only in the last decades has the
synthesis of paracyanogen from different starting materials
and its characterization received a t t e n t i ~ n .Nevertheless,
~ molecular-weight reactions of isocyanogen have been report-
there is still a paucity of experimental data and little is
known about its structure and properties, especially with
respect to its anticipated intrinsic metallic behaviour.
In 1988 the synthesis of another C,N, isomer prepared by
flash vacuum thermolysis (FVT, 773 K at lo-' Torr) of nor-
bornadienone azine in 60% yield was r e p ~ r t e d .Although
~ 2.12, N : 41.37, (CN), calculated (%) C: 46.14, N: 53.86;
initially the C2N2 isomer was identified as diisocyanogen
(CNNC) since only one signal typical for is~cyanides'*~ was
observed in its 13C and 14N NMR spectra at 173 K, the use
of other precursors' and 15N labelling* in combination with
spectroscopic analysis (high-resolution IR, microwave and
'5N NMR spectroscopy), unequivocally revealed that
another C,N, isomer, i.e. isocyanogen (CNCN), is the
primary low-molecular-weight product. Apparently, at some
stage during the thermolysis of the norbornadienone azine,
an efficient isonitrile-nitrile rearrangement takes place
(Scheme 2). Analogous rearrangements have been invoked
previously to rationalize the behaviour of related compounds
under thermolysis conditions.' In this respect, it is note-
worthy that careful spectroscopic analysis (I3C and "N
NMR, 173 K) of the norbornadienone azine pyrolysate
showed that, besides the major product isocyanogen, addi-
tional minor side products, such as hydrogen cyanide (2%),
cyanogen (8%) and ethyne (2%), are present as impurities
even after low-temperature distillation (temperature range
143-173 K).' The identification of these side products pro-
vides evidence that other fragmentation pathways, such as
retro-Diels-Alder cleavage,' are also operative in the ther-
molysis of the norbornadienone azine.
In line with theoretical predictions,' O isocyanogen (CNCN)
was found to be considerably less stable than its isomer
cyanogen (NCCN): It already polymerizes in solution at 193
K ! At this temperature typical isonitrile reactions do not
have a competitive rate." Hitherto, only two distinct low-
ed, i.e. formation of N-cyanodibromoformaldimine by
reaction with bromine' and its chromium pentacarbonyl
complex. l 2 Combustion analysis of pristine paraisocyanogen
[poly(CNCN)] confirmed qualitatively the theoretically
expected C : N ratio of 1 : 1 [experimental (YO)C : 50.15, H :
experimental C : N ratio = 1.4 : 11.' The discrepancy between
the theoretical and experimental data can be attributed to the
incorporation of low-molecular-weight side-products in the
polymer (vide infra). For paracyanogen prepared from several
cyanogen precursors combustion analysis gave C and N
values in the range of 32-34% and 32-44%, re~pectively.~"
Although also for paracyanogen the theoretical and experi-
mental results are at variance, it should be stipulated that it is
well documented that its combustion analysis presents con-
siderable experimental d i f i c ~ l t i e s .Nevertheless,
~ the data
show that both paracyanogen and paraisocyanogen are pri-
marily composed of carbon and nitrogen and may be looked
upon as representative of heteroatom-substituted carbon-
aceous materials. Hence, we were prompted to study in more
detail the molecular structure and properties of paracyano-
gen and paraisocyanogen.

NC:

-
cis trans
Scheme 1 Proposed ladder structure for para~yanogen'*~
FVT
46H6

-&
t Present address: Akzo Research Laboratories Arnhem, P.O. Box Scheme 2 Formation of isocyanogen by FVT of norbornadienone
9300,6800 SB Amhem, The Netherlands. azine5v8
328
Here we report the results of an investigation of both
paracyanogen and paraisocyanogen with polarization
microscopy, wide-angle X-ray powder diffraction (WAXD),
thermogravimetry (TG), and diffuse reflectance Fourier-
transform infrared (DRIFT), solid-state optical (UV-VIS-
NIR, diffuse reflection technique), electron paramagnetic
resonance (EPR) and X-ray photoelectron (XP) spectro-
scopies. In addition, the electrical conductivity of pristine
paraisocyanogen is determined and compared with that of
paracyanogen.
Experimental
Synthesis and Polymerization of Isocyanogen
Isocyanogen was obtained by FVT of norbornadienone azine
at 773 K and Torr as described in detail elsewhere.8
Paraisocyanogen was prepared via two routes. (1) In a high-
vacuum system isocyanogen (52 mg, 1 mmol) was dissolved
in diethyl ether (5 ml) at 173 K and slowly warmed to
ambient temperature during which paraisocyanogen precipi-
tated (yield 60%). (2) In a high-vacuum system isocyanogen
(52 mg, 1 mmol) was sublimed into the gas phase in a reac-
tion vessel (volume 50 ml) at 253 K and warmed to ambient
temperature during which pariasocyanogen precipitated on
the glass surface of the vessel (yield 10-50%). Spectroscopic
analysis revealed that both routes lead to identical paraisocy-
anogen.
Solubility experiments showed that paraisocyanogen, like
p a r a c y a n ~ g e n , ~ - ~is? *an intractable material insoluble in
common organic solvents and concentrated sulfuric acid.
Synthesis and Polymerizationof Cyanogen
Cyanogen was prepared from mercury(I1) cyanide and poly-
merized folowing reported procedures ;4a mercury(I1) cyanide
(4 g, 14.8 mmol) was heated at 713 K in a sealed ampoule
(Pyrex, volume 20 ml) for 24 h. After cooling to ambient tem-
perature the ampoule was opened in a nitrogen atmosphere
and paracyanogen was separated from mercury(0). Pristine
paracyanogen was additionally heated at 473 K for 8 h in
uucuo to remove traces of mercury(0) (yield 95%). The
absence of mercury(0) in paracyanogen was established with
XPS (vide infra).
Characterization of Paraisocyanogen and Paracyanogen
For the T G experiments a Perkin-Elmer TGS-2 equipped
with an autobalance AR-2 was used (temperature program
323-1073 K, heating rate 20 K min-I). DRIFT spectra were
recorded on either a Bio Rad FTS-7 or a Mattson Galaxy
Series FT-IR 5000 spectrophotometer using a diffuse reflec-
tance accessory; the samples were diluted with optically pure
potassium bromide. Powder EPR spectra were recorded on a
Bruker ESP 300 X-band spectrometer operating at 9.6 GHz.
The g values of the peaks and the EPR spectrometer fre-
quency were calibrated against solid diphenylpicrylhydrazyl
radical (DPPH) standard assuming g = 2.0036.13 The EPR
samples were sealed in high-purity quartz capillaries. Solid-
state UV-VIS-NIR spectra were measured on a Varian Cary
5 dispersive spectrometer using a diffuse reflectance acces-
sory (Praying Mantis); the samples were diluted with opti-
cally pure potassium bromide. X P spectra were measured on
a VG Escalab MkII spectrometer with non-monochromated
Mg-Ka X-rays. The powder samples were mounted on a
standard holder using two-sided tape. The absence of inter-
fering signals from the tape was monitored and ascertained
J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90
by the observation of the spectral region in which Si from
silicone present in the tape is expected. Data handling was
performed using the VGS 5250 EDP software package.
Results and Discussion
Polarization Microscopy and X-Ray Powder DifFracton
Polarization microscopy (crossed polarizers, magnification
400 x ) indicates that both materials are amorphous solids.
This is supported by wide-angle X-ray powder diffraction
measurements ; no reflections are discernible ! This shows
unequivocally that neither polymer possesses a three-
dimensional ordering with regular repeat distances in the
range of 2-10 A.14 The absence of reflections typical for
graphite- or poly(acene)-like stacking, anticipated if both
paracyanogen and paraisocyanogen possess a regular ladder-
type structure as previously proposed for the former by
Whangbo et a/.' and Bredas et al.,' suggests that the poly-
mers are composed of small ordered arrays at most. Note
that the latter may well generate diffuse scattered intensity at
wide Bragg angles.
Thermal Stability
Although paracyanogen has been prepared before and has
been the subject of several investigations, few experimental
details concerning its thermal stability are a ~ a i l a b l e . To
~,~
our knowledge only paracyanogen prepared via electro-
polymerization of cyanogen has been subjected to controlled
heat treatements with the objective to assess its conversion
into carbon fibres.I5 To gain insight into the thermal stability
of paracyanogen and paraisocyanogen both polymers were
studied with TG under inert (N2) and thermo-oxidative (air)
conditions. After loss of water of hydration (2 wt.%) at 373 K,
the T G (N2) curve of paracyanogen shows no weight loss up
to 673 K. Above 673 K, gradual thermal degradation and
volatilization of the polymer takes place and is complete at
1123 K ; no residue is found. In contrast, for pristine parai-
socyanogen, which contained ca. 6 wt.% water of hydration,
loss of weight sets in already at 423 K followed by thermal
degradation and volatilization yielding a residue of 18.5 wt.%
at 1123 K. Under thermo-oxidative conditons the onset tem-
perature for weight loss decreases for both polymers
(paracyanogen: 573 K and paraisocyanogen: 373 K), fol-
lowed by gradual thermal degradation and volatilization of
both polymers leaving no residue at 1073 and 873 K, respec-
tively. The differences in thermal behaviour indicate that the
structures of pristine paracyanogen and paraisocyanogen are
markedly different. However, it should be remembered that
paracyanogen, in contrast to paraisocyanogen, is prepared by
heat treatment of mercury(r1) cyanide in a sealed ampoule.
Therefore, we have also studied the effect of a similar heat
treatment of pristine paraisocyanogen at 713 K both in a
sealed ampoule and by isothermal TG (N2). The isothermal
TG (N2) curve showed a weight loss of ca. 50% within the
first 30-40 min of the experiment after which the weight of
the sample remained constant. TG (N2) analysis of heat-
treated paraisocyanogen from the isothermal TG and the
ampoule experiment gave identical TG curves. The heat-
treated polymer is stable up to 773 K. Above this tem-
perature thermal degradation occurs yielding a residue of
16.8 wt.% at 1123 K. Note that the total weight loss found
with TG (N2) after heat treatment in either the isothermal
TG or in the ampoule experiment agrees with the total loss of
weight determined with T G (N2) for pristine paraisocyano-
J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 329

gen. These results suggest strongly that the molecular struc-
ture of pristine paraisocyanogen is altered by the heat
treatment (cf.next section).
Molecular Structure of Paracyanogen and Paraisocyanogen
DRIFTS
To gain insight into the molecular structure of both polymers
DRIFT spectra were measured. The DRIFT spectrum of
paracyanogen contains only broad absorption bands C2170-
2230 cm-' (w), 1750-1000 cm-' (s) and 800-700 cm-' (w),
Fig. l(a)]. The absorption band centred at 2200 cm-' pro-
vides evidence for the presence of pendent isonitrile (-NC)
and nitrile (-CN) groups and the strong broad absorption
'
band centred at 1500 cm- suggests that paracyanogen also
contains imine (-C=N-) and alkene (-C=C-) type
structural units. These data are in excellent agreement with
those previously reported for paracyanogen prepared from a
variety of cyanogen precursor^.^ For pristine paraisocyano-
gen, a markedly different IR spectrum is obtained. Besides
broad absorption bands at 2170-2240 cm-' (w) and 1750-
lo00 cm-' (s) indicating the presence of pendent isonitrile
(-NC) and nitrile (-CN) groups, and imine (-C=N-)-
and alkene (-C-C-) groups, respectively, an additional
strong, broad, featureless absorption band is found in the
region 2500-3500 cm- ' (s) [Fig. l(b)]. Its shape suggests the
presence of a wide variety of amine (-NHR) and carbon-
hydrogen (-CH, and =CH,) groups in considerably differ-
ent molecular environments. Apparently during
polymerization of isocyanogen, the hydrogen-containing
minor side-products, hydrogen cyanide and ethyne, which
still contaminate isocyanogen isolated from the crude pyroly-
sate by low-temperature distillation are efficiently incorpor-
ated in the This is supported by the combustion
data of pristine paraisocyanogen (experimental C : N
ratio = 1.4 : 1) which deviate from the theoretically expected
ratio = 1 : 1 (uide supra). Heat treatment of pristine parai-
socyanogen at 713 K either in a sealed ampoule or with iso-
thermal T G (NJ, leads to a reduction of the absorption
bands at 2500-3500 cm-' and 2170-2240 cm-' and an
increase in the 1750-1000 cm-' band [cf. Fig. l(b): the inten-
sity ratio of 3250 and 1750 cm-' for pristine paraisocyano-
gen is 0.52 and for paraisocyanogen after heat treatment is
0.221. Our data are in agreement with reported results on the
effect of a heat treatment of poly(acrylonitrile).' Upon heat
treatment, a decrease in intensity of the nitrile (-CN)
absorption band concomitant with an increase of the broad
absorption band at the position for imine (-C-N-) and
alkene (-C=C-) type units was observed, which was
attributed to nitrile cyclization. In the case of paraisocyano-
gen, heat treatment undoubtedly will also lead to isonitrile-
nitrile '
rearrangement^.^*'* Presumably, the nitrile
substituents will subsequently cyclize under the high-
temperature conditions.' Note, however, that even after heat
treatment DRIFTS indicates that the structure of heat-
treated paraisocyanogen differs from that of paracyanogen
(Fig. 1). Nevertheless, DRIFTS suggests that both paracyano-
gen and paraisocyanogen are amorphous networks derived
from n-conjugated chains of different length consisting of
coupled imine (-C=N-) and alkene (-C=C-) building
blocks with, especially in the case of paraisocyanogen, a
varying amount of pendent nitrile, isonitrile and amine-type
substituents. Moreover, our DRIFT analysis provides evi-
dence that heat treatment of pristine paraisocyanogen leads
to an increase in unsaturation in combination with the for-
mation of heteroatom-substituted cyclic n-conjugated struc-
tures due to nitrile cyclization.

I
EPR
I I I I I I
3500 3000 2500 2000 1500 1000 500 Powder EPR spectroscopy of pristine paraisocyanogen and
waven umber/cm - ' paracyanogen showed the presence of a single broad reson-
ance with g values of 2.0019 and 2.0017, respectively
(reference DPPH, g value 2.0036) with a moderate peak to
peak linewidth of 6 G at ambient temperature. The g values
indicate the radicals to be carbon ~ e n t r e d . 'The
~ absence of
hyperfine splitting can be attributed to line broadening in the
solid-state samples. In addition, the EPR signal for paracya-
nogen is unsymmetrical, which suggests that the EPR spec-
Q)
trum of paracyanogen is derived from different, but
c - structurally related radical centres. In contrast to the powder
2 EPR spectrum of paracyanogen, the EPR spectrum of pris-
0,- tine paraisocyanogen changed upon exposure of the sample
n
0 to air. Besides a considerable decrease in intensity, a change
in g value to 2.0035 (peak to peak linewidth 8 G at ambient
temperature) was observed. This g value suggests the forma-
tion of iminoxyl or nitrogen radical centres upon exposure to
air.13 Unfortunately, owing to the small amounts of polymer
available, we were hitherto unable to obtain reliable esti-
mates of the spin density of paracyanogen and paraisocyano-
3560 3000 2500 2000 ti00 1000 500
gen before and after exposure to air. Nevertheless, the peak
wavenumber/cm-' to peak linewidths found in the EPR spectra for both pristine
Fig. 1 DRIFT spectra of (a)paracyanogen, (b) (-) pristine para- polymers are indicative of the occurrence of delocalization of
isocyanogen and (-- -) paraisocyanogen after heat treatment at the radical centres and suggest, in agreement with the DRIFT
713 K analysis, that they are composed of n-conjugated structural
330 J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

units.'6a In passing, we would like to remark that as a conse-

quence of the presence of unpaired electrons in both
materials solid-state 3C (CP) MAS NMR measurements
were thwarted.

Electronic Absorption Spectra

Based on the structure of both C2N2monomers and sup-
ported by the DRIFT and EPR analysis, it is expected that
paracyanogen and paraisocyanogen consist of n-conjugated
chains. An estimate of the amount of n-electron conjugation
in paracyanogen and pristine paraisocyanogen was obtained
from solid-state diffuse reflectance UV-VIS-NIR measure-
ments. The spectra show that the level of z-electron delocal-
ization is markedly different for both polymers. Optical band
gaps ( E g ,cut-off energies) of ca. 0.85 and 1.45 eV are derived
from the optical spectra for paracyanogen and pristine para-
isocyanogen, respectively [Fig. 2(a) and (b), solid line].' In 500 1500 2500
accord with the TG and DRIFT results, heat treatment of A/nm
pristine paraisocyanogen leads to considerable changes of the
solid-state UV-VIS-NIR spectrum. For the heat-treated
paraisocyanogen samples prepared either with isothermal TG
(N2, 713 K) or in a sealed ampoule (713 K) an increase in
n-electron conjugation is found; similar UV-VIS-NIR
spectra are obtained with an optical band gap of ca. 0.96 eV
[Fig. 2(b), broken line]. Hence in agreement with our DRIFT
data, solid-state UV-VIS-NIR spectroscopy supports the
conclusion that heat treatment of pristine paraisocyanogen
leads to an increase of n-electron delocalization as a conse-
quence of an increase in unsaturation (extrusion of hydrogen)
in conjunction with nitrile cyclization reactions. In addition,
the difference in optical band gap between heat treated parai-
socyanogen ( E g 0.96 eV) and paracyanogen ( E g 0.85 eV) sup-
ports our contention that even after heat treatment the
structure of paraisocyanogen differs from that of paracyano-
gen.

XPS and Electrical Conductivity Measurements Afnm

The conclusions derived from DRIFT and solid-state UV-
VIS-NIR spectroscopy are corroborated by XPS measure-
ments. In Table 1, the surface element concentrations (atom
Yo)derived from XPS wide-scan spectra and the results of the
decomposition of the C 1s peak shapes (XPS narrow-scan
spectra) are presented. Although 0 is detected besides C and
N, the C : N ratio for both paracyanogen and pristine para-
isocyanogen are in satisfactory agreement with the bulk data
obtained by combustion analysis (XPS: paraisocyanogen, C :
50.7, N: 37.4 and 0: 11.9, C : N ratio = 1.4 : 1; paracyano-
gen, C: 46.8, N : 46.3 and 0:6.9, C : N ratio = 1 : 1).Based on
the observed 0 1s binding energy (0 Is, 534 ev) in com-
bination with the 0 1s peak shape, the oxygen present can be
attributed to physisorbed water (cf. also Thermal Stability
section).I8 A superposition of the C 1s peak shape as well as
the N 1s peak shape for paracyanogen and paraisocyanogen,
respectively, shows directly that, in line with the DRIFT
results, the bonding situation in both polymers is consider-
ably different (Fig. 3). Analysis of the C 1s and N 1s peak
Fig. 2 Solid-state UV-VIS-NIR spectra of (a) paracyanogen,
(-) pristine paraisocyanogen and (- - -)
heat treatment at 713 K
shapes reveals that pristine paraisocyanogen contains carbon
atoms mutiply bonded to nitrogen (C Is, 289 eV, 68%) and
carbon atoms bonded directly to carbon (C Is, 285 eV, 32%).
For paracyanogen the related values are 87% and 13Y0,
respectively. Moreover, it should be stipulated that for pris-
tine paraisocyanogen, both the carbon-to-carbon and
carbon-to-nitrogen contribution to the C 1s peak shape is
symmetrical. In contrast, paracyanogen possesses a distinct
asymmetrical C 1s peak shape; a broad shoulder on the
higher-binding-energy side, i.e. an energy-loss feature, is
observed in the spectrum. The energy-loss feature can be
attributed to interband transitions involving n states which
are excited by some of the photoemitted electron^.'^ Similar
observations also apply to the N 1s peak shape of para-

Table 1 Surface elemental concentration (XPS wide scan) and relative functional group concentrations derived from XPS (narrow scan) C 1s
peak-shape decomposition

surface concentration (atom YO) relative concentration (Yo)

sample C N 0 c=c/c-C" -CN/-NC/-C-N-'

paracy anogen' 46.8 46.3 6.9 13 87
paraisocyanogen 50.7 37.4 11.9 32 68
(CNL 50.0 50.0 -

C 1s binding energy 285 eV.18 C 1s binding energy 289 eV.'* No mercury(0) could be detected by XPS. Theoretical composition.
J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90
30
z
m
X
25
Y 20
3 be represented as amorphous heteroatom-substituted carbon-
8 15
10
I I I I I I
280 285 290 295 300
EbP
X I
I I I 1 I
1
390 395 400 405 41 0 41 5
EbP
Fig. 3 (a) C 1s and (b) N 1s peak shapes obtained with XPS of
(- - -) paracyanogen and (-) pristine paraisocyanogen
cyanogen with respect to that of pristine paraisocyanogen
(Fig. 3). The results strongly support that n-electron conjuga-
tion is much more pronounced in the case of paracyanogen.
The presence/absence of an energy-loss feature in the XPS
spectra of paracyanogen and pristine paraisocyanogen,
respectively, is indicative of the former being a semiconductor
and the latter an i n s ~ l a t o r . 'In
~ agreement with this interpre-
tation, electrical conductivity measurements (four-point-
probe method)2o show that pristine paraisocyanogen and
paracyanogen are an insulator and semiconductor, respec-
tively (paraisocyanogen, ts = 1.0 x S cm-' and paracy-
anogen, Q = 2.9 x S cm-' 'I). To assess if the
experimental Q values for paraisocyanogen and paracyanogen
are in line with anticipated intrinsic Q values the following
crude calculations were made. Using the standard equa-
tion for an intrinsic semiconductor ts = nep with n =
no exp( - E$2k, T ) and E , = 1.45 eV for paraisocyanogen
and 0.85 eV for paracyanogen, under the assumptions that
n o , the number of electrons in the conduction band, is
cm3 and p, the sum mobility of electrons and holes, is l o d 5
cm V - ' s-1,22.23intrinsic Q values of 8.8 x lo-'' S cm-I
and 1.0 x lop9S cm-', respectively, are calculated. Clearly,
for both polymers the estimates are orders of magnitude
lower than the experimental ts value and suggest that extrin-
sic doping either by unintended impurities incorporated
during polymerization or by oxidation in air has occurred. In
the case of pristine paraisocyanogen doping with iodine
vapour gave a substantial increase in electrical conductivity
(298 K, cr = 1.0 x S cm-') which showithat the addi-
tional extrinsic conductivity is p - t ~ p e . ' ~
Conciusions
The results presented show that polymers derived from iso-
cyanogen and cyanogen, respectively, i.e. paraisocyanogen
and paracyanogen, possess different molecular structures and
properties. Spectroscopic analysis shows that n-electron delo-
calization is considerably less in the case of pristine para-
isocyanogen. However, a heat treatment of pristine
33 1
paraisocyanogen leads to an increase in n-electron delocal-
ization presumably due to hydrogen extrusion (increase in
unsaturation) in conjunction with nitrile cyclization reactions
Despite the presence of n-conjugated structures, regular
ladder structures as initially proposed for paracyanogen by
Whangbo et al. are not found.',' Hence, both polymers can
aceous materials.
Experimental contributions of Dr. E. E. Havinga (Philips
I Research Laboratories, Eindhoven, The Netherlands), A.
305 Schouten (Utrecht University, The Netherlands) and E.
Neven (Vrije Universiteit, Amsterdam, The Netherlands) are
gratefully acknowledged.
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Paper 3/05809C; Received 27th September, 1993