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INORGANIC POLYMERS
Introduction
Inorganic polymer science represents an area that has been held back by the synthetic problem of constructing macromolecular chains. However, advances in the
last two decades or so of the twentieth century have led to the preparation of
a variety of new polymers that contain main group elements, transition-metals,
and even lanthanides. It is plausible that some of these new materials, with properties that are difcult or impossible to achieve with existing organic materials, may fulll the requirements of specialized markets; such developments remain an interesting future challenge. Polysiloxanes (silicones) represent the most
well-developed class of inorganic polymers and these materials are discussed in
a separate article (see SILICONES). In addition, although surveyed briey in this
article, more detailed information on POLYPHOSPHAZENES and POLYSILANES and
POLYCARBOSILANES can be found elsewhere in the Encyclopedia. Here we focus on
other main classes of inorganic polymers.

Inorganic Polymers Based on Main Group Elements

Polyphosphazenes. Polyphosphazenes (1) have a polymeric backbone
composed of alternating phosphorus and nitrogen atoms. The side groups, R, can
be alkoxy, aryloxy, amino, alkyl, aryl, inorganic, or organometallic groups. This
large range of accessible structural variations is accompanied by a wide range of
polymer properties that are highly dependent upon the nature of the side groups
(see Table 1).
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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Table 1. Properties of Selected Polyphosphazenesa

Formula

T g , C

T m , C

[NP(O C4 H9 )2 ]n
[NP(On C3 H7 )2 ]n
(NPF2 )n

105
100
96

68, 40

[NP(OC2 H5 )2 ]n
[NP(OCH2 CH2 OCH2 CH2 OCH3 )2 ]n
[NP(OCH3 )2 ]n
(NPCl2 )n

84
84
76
66

7.2 (39)b

[NP(OCH2 CF3 )2 ]n

66

242

[N3 P3 (OCH2 CF3 )5 (CH3 )]n

[N3 P3 (OCH2 CF3 )x (CH2 Si(CH3 )3 )]n
[NP(OCH2 CF3 )(OCH2 (CF2 )x CF2 H)]n
[NP(OC9 H19 )2 ]n
[NP(CH3 )(alkyl)]n
[NP(CH3 )2 ]n
[NP(n C6 H13 )2 ]n
(NPBr2 )n

63
61
60c
56
50d
46
29
15

[NP(OC6 H5 )(OC6 H4 C2 H5 )]n

[NP(OC6 H5 )2 ]n

10e
8

390

[NP(OC6 H4 COOH)2 ]n
[NP(OC6 H4 COOC2 H5 )2 ]n

5
8

127

[NP(OC6 H4 CH3 )(OC6 H4 CHO)]n

[NP(NHCH3 )2 ]n
[NP(OC6 H5 )(OC6 H4 C6 H5 -o)]n
[NP(NHC2 H5 )2 ]n
[NP(CH3 )(C6 H5 )]n
[NP(OC6 H5 )(OC6 H4 C6 H5 -p)]n
[NP(CH3 )(alkyl)]n
[N3 P3 (OCH2 CF3 )4 (C5 H4 FeC5 H4 )]n g
[NP(NHC6 H5 )2 ]n
[NP(OC6 H4 C6 H5 -p)2 ]n
a Refs.

11
14
24
30
37
43
50g
61
91
93

1,23.
the stretched polymer.
c Varies with values x and ratio of side groups.
d Broad, poorly dened transitions.
e Varies with ratio of side groups.
f Complex melting phenomena.
g Ferrocenyl polymer.
b For

143
129

>350

Properties
Elastomer
Elastomer
Hydrolytically unstable
elastomer
Elastomer
Water-soluble elastomer
Elastomer
Hydrolytically unstable
elastomer
Microcrystalline thermoplastic
(lms)
Elastomer
Elastomer
Elastomer
Elastomer
Amorphous gums or waxes
Microcrystalline powder
Wax-like solid
Hydrolytically unstable,
leathery material
Elastomer
Microcrystalline thermoplastic
(lms, bers)
Glass, soluble in aqueous base
Microcrystalline thermoplastic
(lms)
Thermoplastic
Water-soluble glass and
lm former
Glass
Glass, soluble in aqueous acid
Glass
Amorphous gums or waxes
Amber-colored glass
Glassy thermoplastic
Microcrystalline
thermoplastic (high )

Vol. 3

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In addition, the phosphorusnitrogen backbone inherently possesses a

unique range of unusual properties. For example, it is extremely exible which in
turn can give rise to low glass-transition temperatures, particularly in the case
of poly(alkoxyphosphazenes) such as the n-butoxy derivative (T g = 105 C) (1,4).
Furthermore, the backbone is thermally and oxidatively stable, as well as optically
transparent from 220 nm to the near infrared region, which makes it resistant
to breakdown in many harsh environments, as evidenced by the ame-retardant
properties of many polyphosphazenes.
Ring-Opening Polymerization (ROP). The rst polyphosphazene synthesized, poly(dichlorophosphazene) (2), was prepared in cross-linked form by Stokes
at the end of the nineteenth century by the thermal ROP of the cyclic trimer
[Cl2 PN]3 (3) (1). This material, referred to as inorganic rubber, remained a
chemical curiosity because of its intractability and hydrolytic instability until
the mid-1960s when it was shown that if the ROP of pure [Cl2 PN]3 is carried
out carefully, uncross-linked poly(dichlorophosphazene) (2), which is soluble in organic solvents, is formed (5). Subsequent reaction of this highly reactive polymeric
species with nucleophiles has been shown to yield a wide range of hydrolytically
stable poly(organophosphazenes) (eq. 1) (1,68).

(1)

This macromolecular substitution route, used primarily with alkoxides, aryloxides, or primary amines, is largely responsible for the immense structural
diversity of poly(organophosphazenes) and allows the tuning of certain properties and the introduction of others through the choice of nucleophile. Highlights concerning the use of the macromolecular substitution route with 2 and
related materials involve the introduction of side groups, which lead to liquid
crystallinity (see polymer 4) (9), photochromism (10), photocross-linkability (11
13), and the preparation of novel polymers such as (5) with short-chain branching
(14,15).

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The thermal ROP route requires the synthesis and careful purication of
the cyclic trimer [Cl2 PN]3 and the use of elevated temperatures where control of
molecular weight is very difcult and cross-linking can take place at high conversion, which can limit the yield.
Condensation Polymerization. Although several polyphosphazenes have
been commercialized, much work has focused on the development of cheaper
and more convenient methods for making these materials. Also, the reaction
of poly(dichlorophosphazene) with organometallic reagents such as Grignard or
organolithium reagents generally leads to chain cleavage as well as substitution,
and thus macromolecular substitution does not provide a satisfactory route to
polymers with only alkyl and aryl side groups bound by direct P C bonds. To
these ends several promising condensation routes have been developed.
In the early 1980s, a condensation route to polyphosphazenes from phosphoranimines was discovered (eq. 2) (16).

(2)
The polymerization is in fact a chain-growth reaction and allows access to
high molecular weight polyphosphazenes such as poly(dimethylphosphazene) and
poly(methylphenylphosphazene) (2). Methyl deprotonation/substitution of these
polymers as well as electrophilic aromatic substitution of the phenyl substituents
in poly(methylphenylphosphazene) have been developed as versatile strategies
for the derivatization of both of these polymers (eq. 3) (3).

(3)

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An alternative, direct route to uoroalkoxy phosphazene polymers and aryl derivatives which also permits access to block copolymers has been developed (eqs. 4
and 5) (17,18).

(4)

(5)
The development of condensation routes to poly(dichlorophosphazene) have
also been reported. One promising route operates at 200 C (eq. 6) (19).

(6)
In 1995, details of a synthesis of poly(dichlorophosphazene) which operates
at room temperature and allows for good molecular weight control were reported
(eq. 7) (20). It involves the condensation of phosphoranimines in the presence of
cationic initiators such as a PCl5 . The polymerization has been shown to proceed via a cationic chain-growth mechanism that shows living characteristics
(21). Two equivalents of the initiator react with one equivalent of a chlorinated
phosphoranimine to form a reactive ion pair (eg, [Cl3 P N PCl3 ]+ PCl6 ), which
further reacts with monomer to propagate chain growth.

(7)
This synthetic method has been extended to the direct synthesis of
poly(organophosphazenes) as well as the development of star and block copolymers. For example, triarmed star-branched polyphosphazenes (eg, 6) can be synthesized through the initiation of trifunctional phosphoranimines (22). It has
also been shown that the presence of living active sites at the termini of the
polymer chains allows for addition of a second monomer and the formation of
block copolymers (23), such as (7) which is formed through the initiation of a
difunctional linear phosphoranimine and the subsequent introduction of two different monomers (24). These developments offer the prospect of improved routes

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to phosphazene polymers, which may well facilitate more rapid and extensive
commercialization.

Monomer Synthesis. Both the ROP and condensation routes to

poly(dichlorophosphazene) require high purity monomers. For the traditional ROP
process, ultrahigh purity [NPCl2 ]3 is required. The most common method for its
preparation is through the reaction of PCl5 with NH4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 C. The yields
can approach 7080% under specialized conditions, but 50% is more typical (25).
The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl3 P NSi(CH3 )3 . The synthesis of
this compound has been described (21) and is based on a modication of an earlier procedure (26) involving the reaction of PCl5 with LiN(Si(CH3 )3 )2 at 78 C
in hexane. However, the purication required by this method is a challenge and
leads to an overall yield of <40%.
It has also been reported that the reaction of N(Si(CH3 )3 )3 with PCl5 can
be manipulated to maximize yields of either the cyclic trimer (76%) or the pure
phosphoranimine monomer (40%) through variations in reaction conditions (25).
These reactions use milder conditions than previously reported methods, with
higher yields. In addition, the major side product, (CH3 )3 SiCl, can be recycled to
form one of the starting materials, N(Si(CH3 )3 )3 .
N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl3 , ((CH3 )3 Si)2 NH,
and Grignard reagents by way of a three-step process, with typical yields of
6070%. These precursors are also accessible via a one-pot synthesis, which
requires only isolation of the nal product with yields of about 75% (3).
Uses. Some of the most useful polyphosphazene derivatives are
uoroalkoxy derivatives, and amorphous copolymers are very useful as
ame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have
found aerospace and automotive applications. Polymers such as the amorphous
comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1).

Vol. 3

INORGANIC POLYMERS

35

Polyphosphazenes are also of interest as biomedical materials and bioinert,

bioactive, membrane-forming, and bioerodable materials (1).

Polysilanes
Properties. Since the rst reports of soluble and processible polysilanes
(9) in the late 1970s, these macromolecules have attracted widespread interest
from both a fundamental and an applied perspective (1,2729). The use of Wurtz
coupling has allowed the preparation of a range of polymers with alkyl or aryl substituents at silicon that are high in molecular weight with M n > 105 . Since 1980,
there has been a remarkable growth in interest concerning these polymers and
they have been found to possess a variety of fascinating properties. The backbone
of silicon atoms gives rise to unique electronic and optical properties.

One of the most remarkable features of the all-silicon backbone is that it

leads to the delocalization of electrons, a phenomenon which is virtually unknown in carbon chemistry (30). This can be understood in terms of the nature
of the molecular orbitals associated with the Si Si bonds. These are more diffuse than those associated with C C bonds as they are constructed from higher
energy 3s and 3p atomic orbitals. This leads to signicant interactions between
the adjacent Si Si bonds along a polysilane chain, a situation analogous to
that for the bonds in -delocalized polymers such as polyacetylene. Thus, a
band model is more appropriate than a localized model (1,28). As a consequence
of the delocalization of electrons, the transition, which occurs at 220 nm
in (CH3 )3 Si Si(CH3 )3 , moves to lower energy as the number of silicon atoms in
the chain increases. In the high polymers, the band-gap transitions occur
in the near uv region at ca 300400 nm (Table 2). The lowest absorption bands of
polysilanes have also recently been assigned to excitonic rather than interband
transitions (32). The electron delocalization also leads to appreciable electrical
conductivity following doping. For example, conductivities of up to 0.5 S/cm have
been reported for polysilastyrene (10), after doping with AsF5 (1). In addition,
many of the polymers are thermochromic as the conformations adopted by the
polymer change with temperature, which alters the degree of -delocalization
along the main chain. Because of their low energy transitions, polysilanes

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INORGANIC POLYMERS

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Table 2. Ultravioletvisible Absorption Data for Typical Polysilanesa,b

R2

max , nm

/SiSi

C3 H7
C4 H9
n
C6 H13
n
C12 H25
C2 H4 -C6 H5
c
C6 H13
n
C3 H7
n
C4 H9
n
C6 H13
n
C14 H29
n
C6 H13
n
C8 H17
C6 H5
p-C6 H4 CH3
p-C6 H4 OCH3
p-C6 H4 On C6 H13
p-C6 H4 C6 H5
-naphthyl
p-C6 H4 C2 H5
p-C6 H4 n C4 H9
p-C6 H4 s C5 H11
p-C6 H4 t C4 H9
p-C6 H4 n C6 H13
m-C6 H4 n C6 H13
p-C6 H4 n C6 H13

306
304
306
309
303
326/320
310
314
316/317
318
322
318
341
337/338
344
354
352
350
390
395
390
376
397
400
394

5600

R1
CH3
CH3
CH3
CH3
CH3
CH3
n
C3 H7
n
C4 H9
n
C6 H13
n
C14 H29
n
C3 H7
n
C6 H13
CH3
CH3
CH3
CH3
CH3
CH3
p-C6 H4 C2 H5
p-C6 H4 n C4 H9
p-C6 H4 s C5 H11
p-C6 H4 t C4 H9
p-C6 H4 n C6 H13
m-C6 H4 n C6 H13
p-C6 H4 n C6 H13
a In

n
n

5100
5000
9950
7390
8400
9700
8400
10600
8785
9300
8600
8180
5400
4000
2800
10200
26600
16200
3400
23300
21300
18600

solution.
28 and 31.

b Refs.

are photosensitive and have attracted considerable attention as photoresist materials in microlithography (1,27,28).

Synthesis. The rst report of a soluble polysilane appeared in 1978 and

the material was prepared by the treatment of a mixture of organodichlorosilanes
with sodium metal (33). Instead of only the expected cyclic oligomers, a polymeric product, termed polysilastyrene (10), was formed. Poly(dimethylsilane) had
been previously prepared as a highly crystalline insoluble material (1,27,28). The
introduction of phenyl groups in the random copolymer reduces the crystallinity
and allows the material to be soluble and processible.

Vol. 3

INORGANIC POLYMERS

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The main method used to synthesize polysilanes involves the

thermally-induced Wurtz coupling reaction of organodichlorosilanes with
alkali metals (eq. 8). Although improvements in this process have been reported
(eg, the use of ultrasound), the harsh conditions for this reaction tend to limit the
side groups that can be successfully introduced to nonfunctionalized alkyl and
aryl units and makes scale-up unattractive (1).

(8)
Because of these limitations, considerable effort has been focused on the
development of new synthetic routes to polysilanes. Transition-metal-catalyzed
dehydrogenative coupling, discovered in 1985 (eq. 9) (34), is potentially very attractive; however, the molecular weights of the polysilanes formed to date are
generally quite low (M n < 8,000). The catalysts used for these coupling reactions
are usually titanocene or zirconocene derivatives (34,35).

(9)
The catalytic dehydrogenation route yields novel polysilanes with Si H functionalities, which are of interest as ceramic precursors (36). In addition, it has been
shown that a variety of new side groups can be introduced using a derivatization
approach (eq. 10) (37).

(10)
In 1991, a novel ROP route to polysilanes was reported (eq. (11)) (38). The key
to this approach is to take readily accessible octaphenylcyclotetrasilane, which
is too sterically crowded to undergo ROP, and to replace some of the phenyl
groups by smaller methyl substituents (via a two-step process) to make the ring
polymerizable.

(11)

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Another route to polysilanes that involves the anionic polymerization of disilabicyclooctadienes, which function as sources of masked disilenes (eq. 12), has
been described (39,40). Amphiphilic block copolymers formed by this anionic route,
such as poly(1,1-dimethyl-2,2-dihexyldisilene)-b-(2-hydroxyethyl methacrylate),
undergo self-assembly to form micelles (41).

(12)

Uses. The delocalization of electrons in polysilanes gives rise to unique

electronic and optical properties. Also, several polysilanes have been found to
function as useful thermal precursors to silicon carbide bers and these materials have attracted attention with respect to microlithographic applications and as
polymerization initiators (1,27,28). The use of these materials as hole transport
layers in electroluminescent devices has also been explored (42). Indeed, the photoconductivity of poly(methylphenylsilane) doped with C60 has been studied and
has been found to be comparable with the best materials available (43).

Polygermanes and Polystannanes

Properties. The remarkable properties of polysilanes has led to signicant
interest in the development of polymer chains based on the heavier Group 14
elements, germanium and tin.
Studies of polygermanes indicate that the delocalization is even more extensive than for polysilanes and that the band-gap transition for the high
polymers is signicantly red-shifted by ca 20 nm in comparison to the silicon analogues (44,45) (Table 3). Other studies have shown that these materials possess
semiconductive behavior upon oxidative doping (49) as well as signicant nonlinear optical behavior (50) and thermochromicity (45).
High molecular weight polystannanes possess electrons that are extensively delocalized as illustrated by the band-gap transition, which occurs at
384388 nm for poly(dialkylstannanes) (in THF) and at even higher wavelengths
for some poly(diarylstannanes) (Table 3) (48,51). In addition, exposure of thin lms
of the polymers to the oxidant AsF5 leads to signicant electronic conductivities of
ca 0.010.3 S/cm (52). Polystannanes are highly photosensitive and exhibit photobleaching behavior, and on uv-irradiation depolymerize to yield cyclic oligomers.
The materials are thermally stable to 200270 C in air and, at more elevated
temperatures, function as interesting precursors to SnO2 (52).
Synthesis. Polygermanes (11) were prepared in the mid-1980s by Wurtz
coupling techniques similar to those used to prepare the silicon analogues (eq. 13)
(1). A variety of alkyl and aryl derivatives can be prepared by this method but the
harsh reaction conditions are not tolerant of many functional groups (53).

Vol. 3

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Table 3. Ultravioletvisible Absorption Data for Some Typical Polygermanes

and Polystannanes [ER1 R2 ]n a
E

R1

R2

max , nm

Ge
Ge
Ge
Ge
Ge
Ge
Ge
Ge
Ge
Ge
Ge
Ge
Sn
Sn
Sn
Sn
Sn
Sn

CH3
CH3
CH3
CH3
CH3
CH3
C2 H5
n
C3 H7
n
C4 H9
n
C5 H11
n
C6 H13
C6 H5
p-C6 H4 t C4 H9
p-C6 H4 n C6 H13
o-C6 H4 C2 H5
p-C6 H4 On C4 H9
o-C2 H5 -p-On C4 H9 C6 H4
p-C6 H4 N(Si(CH3 )3 )2

C6 H5
p-C6 H4 F
p-C6 H4 CF3
p-C6 H4 CH3
m-C6 H4 (CH3 )2
p-C6 H4 OCH3
C2 H5
n
C3 H7
n
C4 H9
n
C5 H11
n
C6 H13
n
C4 H9
p-C6 H4 t C4 H9
p-C6 H4 n C6 H13
o-C6 H4 C2 H5
p-C6 H4 On C4 H9
o-C2 H5 -p-n C4 H9 -C6 H4
p-C6 H4 N(Si(CH3 )3 )2

332b /327c
336b
332b
326b
330b
338b
293c
312c
325c
327c
325c
337c
432d
436d
468d ,e
448d
506d
450d

a All

values were measured in THF unless otherwise noted.

via demethanative coupling (46).
c Synthesized via electrochemical polymerization (47).
d Synthesized via catalytic polymerization (48).
e Value obtained on a thin lm of the polymer.
b Synthesized

(13)
Dehydrocoupling has been investigated, but has proven relatively unsuccessful (54). Electrochemical reduction of halogermanes has proven somewhat successful and has provided a route to poly(germanegermane) and poly(germanesilane)
copolymers (47,55). The ruthenium catalyst, Ru(P(CH3 )3 )4 (CH3 )2 , can be employed in the demethanative coupling of trimethylgermane, which gives relatively
high molecular weight polygermanes under mild conditions (25 C) (eq. 14) (46,56).

(14)
Early attempts to generate polystannanes by Wurtz coupling of organodichlorostannanes have yielded only low molecular weight oligomers and
reduction products. The rst high molecular weight materials were made using

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transition-metal-catalyzed dehydrogenative coupling of secondary stannanes

R2 SnH2 (eq. 15) (51). Yellow polystannanes (12) (R = n-butyl, n-hexyl, or n-octyl)
of substantial molecular weight (up to M w = ca 96,000, M n = ca 22,000)
were prepared using various zirconium catalysts. This method is applicable
to the preparation of poly(diarylstannanes) possessing solubilizing substituents
(48,57). Interestingly, a change in catalyst from zirconocene-based systems to
HRh(CO)(P(C6 H5 )3 )3 has been shown to lead to highly branched polystannane
structures (58).

(15)

Uses. Both polygermanes and polystannanes may nd applications because of their unique optical, electronic, and chemical properties. Some of these
potential uses include photoresist layers (44,59,60), third-order nonlinear optical
materials (50), charge transport polymers (61,62), photoconductors, microlithographic materials (63), and photoinitiators (59).
Boron-Containing Polymers
Boron-containing polymers are of considerable intrinsic interest, as possible reactive intermediates and as precursors to boron-based ceramics (6469). The synthesis of polyborazines (13) (M w up to ca 7600, M n up to ca 3400) via thermally induced
dehydropolymerization of borazines (eq. 16) has been reported (68). The polymers
were isolated as white solids and characterization suggested the presence of a
signicantly branched structure. Pyrolysis at 1200 C yielded white turbostratic
boron nitride in 8593% yield.

(16)
A wide range of novel polymers with boron in the backbone have been prepared by means of boration polymerizations (65,7082). Diynes can be polymerized by hydroboration (70,71), phenylboration (65), and haloboration (72) to yield
polymers (14),(15), and (16) (eq. 17). When an appropriate aromatic or heteroaromatic diyne is used, the resulting polymers have been shown to have extended
-conjugation through the vacant p-orbital of the boron atom (73,74). In fact, several have been shown to exhibit blue uorescence emission.

Vol. 3

INORGANIC POLYMERS

41

(17)
Diisocyanates have been shown to undergo haloborationphenylboration
polymerization to give halosubstituted polymers (17) (75). They also undergo
alkoxyboration in the presence of mesityldimethoxyborane to produce poly(boronic
carbamates) (18) (eq. 18) (76).

(18)
Dicyano
compounds
undergo
hydroboration
to
produce
poly(cyclodiborazanes) (19), which have proven relatively stable towards air and
thermal oxidation (eq. 19) (7779). Some examples have been prepared where
the dicyano compound allows for incorporation of a charge transferred structure
(80). These exhibit extended -conjugation through the cycloborazane unit.

(19)

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Finally, the polycondensation reaction between bifunctional Grignard

reagents and aryldimethoxyboranes, carried out under a nitrogen atmosphere,
in THF, gives rise to poly(phenylene-boranes) (20) (eq. 20) (83). The conjugated
polymers may have potential applications in electronic devices such as LEDs.

(20)
Transition-metal-catalyzed dehydrocoupling of phosphineborane adducts
(21) has been shown to give rise to high molecular weight polyphosphinoboranes
(22) (84). In the 1950s and 1960s, several claims of the synthesis of polyphosphinoboranes (22) were made (eq. 21). The main route studied was the thermal
dehydrocoupling of R2 PHBH3 adducts at 200 C and above; however, structural
characterization of the polymers was minimal and reported yields and molecular
weights were very low (85,86).

(21)
The dehydrocoupling of various adducts (21) has now been studied in
the presence of various catalysts, such as RhCl3 , [Rh( Cl)(1,5-cod)]2 , and
[Rh(1,5-cod)2 ]+ (87). The bulky adduct (21) (R1 = R2 = C6 H5 ) was shown to undergo dehydrogenative coupling to form only a linear dimer or a mixture of the
cyclic trimer and tetramer, depending upon the temperature used. However, primary phosphineborane adducts, such as C6 H5 PH2 BH3 and iC4 H9 PH2 BH3 , were
found to undergo catalytic dehydrogenative polymerization under similar conditions to yield soluble polyphosphinoboranes (22) (eq. 22). When the polymerization
is carried out in solution, the resulting polymers are low in molecular weight (eg,
M w 5600 for R = C6 H5 ) whereas the neat polymerization affords high molecular
weight phosphorusboron polymers (eg, M w 31,000 for (22) R = C6 H5 ). These
polymers are air and moisture stable in the solid state, and detailed studies of
the physical properties have yet to be conducted but the novel phosphorusboron
backbone allows for interesting possibilities such as low temperature exibility,
ame retardancy, and ceramic formation.

Vol. 3

INORGANIC POLYMERS

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(22)

Polycarbophosphazenes
Polycarbophosphazenes possess a backbone of phosphorus, nitrogen, and carbon
atoms and can be regarded as derivatives of classical polyphosphazenes (1) in
which every third phosphorus atom is replaced by carbon. The rst examples of
these materials were discovered in 1989 (88). Thermal ROP of a cyclic carbophosphazene was used to prepare the chlorinated polymeric species (23), which undergoes halogen replacement reactions with nucleophiles such as aryloxides and
aniline to yield hydrolytically stable poly(aryloxycarbophosphazenes) (24) (M w =
ca 105 , M n = 104 ) (eq. 23) (8891). The polymer backbone in these materials was
found to be less exible than in classical polyphosphazenes. For example, the halogenated polymer (23) possesses a T g of 21 C compared to a value of 66 C for
poly(dichlorophosphazene) (2).

(23)
The reaction of (23) with alkylamines has also been studied (91). The resulting poly(alkylaminocarbophosphazenes) are sensitive to hydrolysis. However, arylamino derivatives are moisture stable and, in addition, a novel, regioselectively
substituted polymer (25) was successfully prepared via the sequential reaction
with NH(C6 H5 )2 and triuoroethoxide anions (eq. 24).

(24)

44

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SulfurNitrogenPhosphorus Polymers
Sulfurnitrogenphosphorus polymers possess backbones that can be regarded
as compositional hybrids of those present in sulfurnitrogen polymers, such as
the solid-state polymer poly(sulfur nitride) [SN]x or polyoxothiazenes [RS(O) N]n
and classical polyphosphazenes, [R2 P N]n (1) (92). Poly(sulfur nitride), [SN]x , possesses remarkable properties such as electrical conductivity at room temperature
and superconductivity below 0.3 K (93). [SN]x is insoluble and has a polymeric
structure in the solid state with interchain SS interactions. As these interactions are crucial to the properties of the material, [SN]x is best regarded as a
solid-state polymer rather than a polymeric material with discrete macromolecular chains of the type discussed in this article.
The rst well-characterized examples of sulfurnitrogenphosphorus materials, polythiophosphazenes, were reported in 1990 (94). These polymers
were prepared via the thermal ROP of a cyclothiophosphazene (eq. 25). This
yielded the hydrolytically sensitive polythiophosphazene (26) with a backbone of
three-coordinate sulfur(IV), nitrogen, and phosphorus atoms. Although reaction of
(26) with nucleophiles such as aryloxides yielded materials (27) with improved hydrolytic stability, degradation was still rapid except where very bulky substituents
such as o-phenylphenoxy were present.

(25)
Although the backbone of polythiophosphazenes appears to be quite fragile,
a particularly interesting feature of the substitution reactions of (26) is that the
S Cl bond is much more reactive than the P Cl bonds. Regioselective substitution at the sulfur center is possible and yields macromolecules (29) with different
aryloxy substituents at sulfur and phosphorus (eq. 26) (94,95).

(26)
In 1991, another class of sulfurnitrogenphosphorus polymers, polythionylphosphazenes, were reported (96,97). These materials, which possess
four-coordinate sulfur(VI) atoms in the backbone, possess improved stability and
were prepared by a thermal ROP of cyclic thionylphosphazenes (30), with either chlorine or uorine at the sulfur(VI) center, at 165180 C (eq. 27) (98). An

Vol. 3

INORGANIC POLYMERS

45

ambient temperature synthesis involving initiation by Lewis Acids such as GaCl3

has been subsequently developed (99).

(27)
The halogenated polythionylphosphazenes (31) that are formed in these ROP
reactions (together with small quantities of macrocyclic byproducts) are quite sensitive to hydrolysis but a variety of moisture-stable derivatives have been prepared
by reaction of this species with aryloxides or amines (100102). Mixed substituent
aryloxyalkoxy polymers have also been prepared (92). Interestingly, with aryloxides, regioselective substitution at phosphorus is observed and in the resulting
polymers (32) the sulfur(VI)-halogen bond remains intact. Remarkably, this regioselectivity is the exact reverse of that detected for the polythiophosphazenes
described earlier where the sulfur(IV)-halogen bond is more reactive. In contrast
to the reactions with aryloxides, reaction with primary or secondary amine nucleophiles leads to substitution at both the phosphorus and the sulfur(VI) centers to
give poly(aminothionylphosphazenes) (33) (102,103).

Ab initio calculations on isotactic polythionylphosphazene (31) (X = Cl or F)

indicate a localized electronic structure for the polymer backbone and predict
that a cistrans helical conformation is the most energetically favorable for
isolated macromolecules (104). This is in contrast to the analogous classical
polyphosphazene (1) where a trans-planar conformation is preferred. Studies of
the properties of the polythionylphosphazenes also reveal signicant differences
in thermal transition behavior and polymer morphology compared to classical
polyphosphazenes. For example, the polymer [NSOF{NP(OC6 H5 )2 }2 ]n is an amorphous elastomer (T g = 15 C), whereas the analogous classical polyphosphazene
[NP(OC6 H5 )2 ]n is a microcrystalline thermoplastic (T m = 390 C, T g = 6 C). The
T g s of the uorinated polythionylphosphazenes are lower than those of the analogues with chlorine at sulfur. For example, for (31) (X = F) T g = 56 C whereas
for (31) (X = Cl) T g = 46 C (101). Poly(aminothionylphosphazenes) possess high
gas permeability and have found utility as matrices for phosphorescent dyes for
oxygen sensing applications (105).
Also noteworthy is an interesting condensation route reported which leads
to polymers with backbones of alternating S(O) N and P N units (106).

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Preliminary reports of the rst polythiazylphosphazenes (34), which possess

three-coordinate sulfur(III) atoms, have appeared (eq. 28) (107). These materials
would represent true hybrids of poly(sulfur nitride) and polyphosphazenes and
further developments in this area should prove to be particularly interesting.

(28)

Polyoxothiazenes
Partially characterized polyoxothiazenes were briey reported in the early 1960s
(108). However, in 1992 the rst well-characterized examples (35) with alkyl or
aryl substituents at sulfur were described (109). These polymers, which possessed
estimated molecular weights of M w = ca 105 and M n = ca 104 , were synthesized via the condensation polymerization of N-silylsulfonimidates at 120170 C
over 28 days (eq. 29). These reactions are catalyzed by added Lewis acids (eg,
BF3 O(C2 H5 )2 ) and bases (eg, uoride). By using a mixture of different sulfonimidates, random copolymers such as [CH3 S(O) N]m [C6 H5 S(O) N]n were also successfully prepared. Free sulfonimidates were also found to thermally condense
to yield poly(organooxothiazenes) at lower temperatures than their N-silyl analogues (eq. 29) (109,110).

(29)

Polyoxothiazenes appear to be highly polar. For example, [CH3 S(O) N]n

is soluble in DMF, DMSO, hot water, and concentrated H2 SO4 . Studies of
the thermal transition behavior of these materials have indicated that they
are amorphous, which is consistent with an atactic structure. Interestingly,
the T g of [CH3 S(O) N]n is ca. 60 C, which is dramatically higher than for
[(CH3 )2 P N]n (T g = 46 C). This suggests a much less exible backbone for
polyoxothiazenes compared to polyphosphazenes, as might be expected from

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47

studies on polythionylphosphazenes (vide supra). Thermogravimetric analysis

(TGA) showed that the polymers are stable to weight loss up to ca 270 C
(at a heating rate of 10 C/min). Theoretical studies on [CH3 S(O) N]n have
indicated that a cistrans helical conformation is the most stable for this polymer
(110).

Inorganic Polymers Based on Transition Elements

Ferrocene-Based Polymers. The excellent thermal stability and interesting physical (eg, redox) properties associated with the ferrocene moiety have
led to extensive efforts aimed at the incorporation of this unit into polymer structures. The inclusion of this moiety in the side-group structure of polymers has
been very successful and requires only minor modications of previously established synthetic methodologies. For example, poly(vinylferrocene) (36) can be prepared via the free radical addition polymerization of vinylferrocene (111). The
incorporation of ferrocene moieties into the main chains of polymers where the
metal atoms are separated by a considerable distance has also been achieved.
The extensive organic chemistry of the metallocene nucleus has allowed for the
preparation of well-dened difunctional ferrocenes that have been used in controlled polycondensation reactions to yield well-dened products of appreciable
molecular weight. Examples of products derived from such reactions involve the
poly(arylenesiloxaneferrocenes) (eg, 37) (112), ferrocene-containing polyesters
(113), and novel accordian type polymers (114,115).

The versatile chemistry of the ferrocenyl moiety has also allowed for the
preparation of a large number of dendrimeric structures with this group at the
periphery (116118). A series of dendrimers based upon polypropylenimine cores
have been reported (119,120) and star-shaped macromolecules with ferrocene
units at the periphery have been produced (121), as well as amido-ferrocene dendrimers (eg, 38) (122). A convergent approach has allowed for the synthesis of
dendrimers (39) for which the ferrocene units at the periphery display electronic
interaction (123).

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49

In contrast, very few examples of polymers with ferrocene units in close proximity, which could take advantage of interactions between the metal atoms, have
been prepared. The development of materials with interesting physical (eg, electronic and/or magnetic) properties might be anticipated based on the properties
of molecular species in which two ferrocene units are linked close together. Thus,
in such systems the iron atoms can interact and in some cases yield delocalized,
mixed valent species upon one-electron oxidation, even when the metal atoms are
up to 0.7 nm apart (124,125). Work in this eld has largely yielded low molecular
weight (M n  10,000) and often poorly dened materials (126). For the synthesis
of well-characterized polymers (M n < ca 11,000) with main chains of ferrocene
groups and vinylene, divinylene, or oligovinylene units see Reference 127.

Polyferrocenylenes
A typical early route to polyferrocenylenes (40) with M n < 5000 involved polycondensation processes such as the recombination of ferrocene radicals generated via the thermolysis of ferrocene in the presence of peroxides. However, these materials have been found to possess other fragments such as
CH2 and O in the main chain (128,129). More structurally well-dened polyferrocenylenes (40) (M n < 4000) have been prepared (130) via the condensation reaction of 1,1-dilithioferroceneTMEDA (tetramethylethylenediamine) with
1,1-diiodoferrocene and, signicantly, the reaction of 1,1 -dihaloferrocenes with
magnesium (eq. 30) has been shown to afford low molecular weight (M n = 4600
for soluble fractions) materials with appreciable crystallinity (131). In the latter
case, oxidation with 7,7,8,8-tetracyanoquinodimethane (TCNQ) afforded doped
polymers that were delocalized on the Mossbauer time scale (ca 10 7 s) at room
temperature and which possessed electrical conductivities of up to 10 2 S/cm.

(30)

Polyferrocenylsilanes
Properties. Polyferrocenylsilanes possess a backbone of alternating ferrocene and organosilane units. Since the early 1990s when the rst high molecular weight, well-characterized examples were prepared by a ROP approach,
considerable effort has been directed towards understanding the properties of
polyferrocenylsilane materials, the vast majority of which are soluble in common organic solvents (132,133). It was noted early on that electrochemistry of
the high polymers such as (41) (R = R = CH3 ) possess two reversible oxidation
waves in a 1:1 ratio (132,134). This provided clear evidence for the existence of
interactions between the iron atoms, and led to the proposal that initial oxidation

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occurred at alternating iron sites along the main chain. Work on model oligomers
with between two and nine ferrocene units has provided clear evidence in support of this postulate (135). Similar electrochemical behavior has subsequently
been detected for a range of other polyferrocenylsilanes (134). Oxidative doping
of poly(ferrocenyldimethylsilane) with I2 has been shown to yield semiconducting materials ( = ca 10 4 S/cm) whereas the pristine materials are insulating
( = ca 10 14 S/cm) (133). A report indicates that several tetracyanoethylene
(TCNE)-oxidized low molecular weight polyferrocenylsilanes (M w = ca 1500) show
electron delocalization on the Mossbauer time scale (ca 10 7 s) and also ferromagnetic ordering at low temperatures (136). Studies of high molecular weight
M w > 105 analogues have not reproduced this behavior (137). Thin lms of the
homopolymers and block copolymers with organic or inorganic co-blocks are attracting attention for numerous applications, such as chemomechanical sensors,
electrochromic materials, electrode mediators, variable refractive index materials, hole transport layers, charge dissipation coatings for dielectrics, lithographic
resists, and photonic band-gap materials (133,138144).

The polymers also exhibit interesting morphology and several of the symmetrically substituted derivatives will crystallize. For example, the dimethyl derivative (41) (R = R = CH3 ) is an amber, lm-forming thermoplastic and possesses
a T m at 120145 C depending on crystallite size and a T g at 33 C whereas, in
contrast, the n-hexyl analogue (41) (R = R = n-hexyl) is an amber, gummy amorphous material with a T g of 26 C (133). The packing in the crystalline regions of
polymer (41) (R = R = CH3 ) has been shown to be analogous to that of a linear pentamer (135,141,142). In addition, as the iron atom in ferrocene acts as a molecular
ball-bearing, this gives these polymers a large degree of conformational exibility
and consequently T g s are lower than might be expected for polymers with such a
bulky unit in the main chain (133) (Table 4).
Several polyferrocenylsilanes can be fabricated in the melt (eg, R = R =
CH3 above 150 C) (Fig. 1). Polyferrocenylsilanes have been found to exhibit excellent thermal stability to weight loss (up to 350400 C) and have been shown
to yield interesting composites containing Fe nanoparticles at 5001000 C (145
147). Controlled cross-linking of the polyferrocenylsilanes can be used to make
magnetic ceramic lms and monoliths with the same shape as the polymer precursor as well as solvent-swellable, redox-active gels (148,149). The solution properties of polyferrocenylsilanes such as the dimethyl derivative (41) (R = R = CH3 )
have been well-characterized by light-scattering experiments and viscometry and
MarkHouwink parameters have been established (150).

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Table 4. Thermal Transition and gpc Molecular Weight Data for Selected
Polyferrocenylsilanesa
R/OR
H
CH3
C2 H5
n
C3 H7
n
C4 H9
n
C5 H11
n
C6 H13
CH3
CH3
CH3
CH3
CH3
CH3
CH3
OCH3
OC2 H5
OCH2 CF3
On C4 H9
On C6 H13
On C18 H37
OC6 H5
(OCH2 CH2 )OCH3
CH3

R /OR

T g (T m )b , C

Mn c

PDId

H
16 (165)
e
e
5
CH3
33 (122143)
3.4 10
1.5
C2 H5
22 (108)
4.8 105
1.6
n
C3 H7
24 (98)
8.5 104
2.7
n
C4 H9
3 (116,129)
3.4 105
2.6
n
C5 H11
11 (80105)
3.0 105
1.6
n
C6 H13
26
7.6 104
1.5
H
9 (87, 102)
4.2 105
2.0
CH2 CH2 CF3
59
8.1 105
3.3
CH CH2
28
7.7 104
2.1
n
C18 H37
1 (16)
5.6 105
2.5
C6 H5
90
1.5 105
2.0
Fc f
99
7.1 104
2.3
CH2 CH2 CH2 Cl
27
2.7 105
1.5
OCH3
19
1.5 105
1.9
OC2 H5
0
3.8 105
2.1
OCH2 CF3
16
2.2 105
1.2
On C4 H9
43
3.9 105
2.1
On C6 H13
51
0.9 105
2.4
On C18 H37
(32)
2.3 105
2.2
OC6 H5
54
2.3 105
2.0
(OCH2 CH2 )OCH3
53
1.0 105
2.6
(OCH2 CH2 )x OCH3 g 69, 72h 5.6 104 , 1.9 105 2.3, 2.2

a Refs.

133 and 143.

data collected at a heating rate of 10 C min 1 .
c GPC data and molecular weight values are relative to polystyrene standards. Although in this
case gpc provides only molecular weight estimates, absolute determinations of M w by static light
scattering for several polymers have indicated that gpc underestimates the real values by a factor
of 2 (144).
d PDI = M /M .
w
n
e Insoluble polymer.
f Fc = (-C H )Fe(-C H ).
5 4
5 5
g x 8.
hTwo different molecular weight samples.
b DSC

Water-soluble polyferrocenylsilanes have also been prepared and these possess, for example, oligoethoxy or ionic side chains (151,152). These materials can be
used in layer-by-layer assembly processes to form superlattices with a range of potential applications (153). Novel random copolymers (42) with oligosilane spacers
have also been prepared by using a thermal copolymerization process (154,155).
These polymers possess interesting photophysical and charge transport properties. Indeed, the skeletons of the polysilane segments can be selectively cleaved
using uv light because of the photosensitive nature of the Si-Si bond. Block copolymers containing polyferrocenylsilane blocks (vide infra) have demonstrated interesting self-assembly behavior and are of interest for nanostructure applications
(156). For example, cylindrical worm-like micelles with a polyferrocenylsilane core

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Fig. 1. Samples of melt processed polyferrocenylsilanes.

and a polysiloxane corona can be fabricated and are of potential use as semiconducting nanowires and as etching resists in nanolithography (157).

Synthesis.
Ring-Opening Polymerization. Early attempts to prepare macromolecules
in which the ferrocene units are separated via an organosilane spacer group focused on the use of polycondensation reactions. Partially characterized, impure
polyferrocenylsilanes were prepared via the reaction of dilithioferrocene with
organodichlorosilanes. The molecular weights of 14007000 reported for these
materials are characteristic of polycondensation processes where exact reaction
stoichiometries are virtually impossible to achieve because one reactant, in this
case dilithioferrocene, cannot be readily prepared in pure form (116).
In 1992, the rst synthesis of high molecular weight polyferrocenylsilanes
(41) (M w = 105 106 , M n > 105 ) via a thermal ROP route was reported (132,158).
This process involved heating silicon-bridged [1]ferrocenophanes (43) in the melt
at 130220 C (eq. 31). The presence of a single-atom bridging the ferrocene unit
in the monomer leads to a strained structure in which the planes of the cyclopentadienyl rings are tilted with respect to one another by an angle of ca 21 . In
contrast, in ferrocene the cyclopentadienyl rings are parallel. The presence of
strain in the ferrocenophane, which has been measured to be ca 80 kJ/mol for
(43) (R = R = CH3 ), is believed to provide the driving force for the ROP process
(132,158).

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(31)
Since this initial discovery, a wide range of silicon-bridged [1]ferrocenophanes with either symmetrically or unsymmetrically substituted silicon atoms
have been prepared and similarly polymerized (Table 4). Polymerization of a mixture of different silicon-bridged [1]ferrocenophanes has also been shown to yield
random copolymers (159).
Silicon-bridged [1]ferrocenophanes undergo living anionic ROP using initiators such as n-C4 H9 Li in THF (160,161). This has permitted the synthesis of
polyferrocenylsilanes with controlled molecular weights and narrow polydispersities and has also allowed the preparation of the rst block copolymers containing
skeletal transition-metal atoms (160,161). Block copolymers such as (44) have
been prepared with other monomers that undergo anionic polymerization such as
cyclic siloxanes (see eq. 32) or organic monomers such as polystyrene and isoprene
(161,162). The resulting block copolymers undergo phase separation in the solid
state and, in solution, micellar aggregates are formed (156,163).

(32)
Also, the transition-metal-catalyzed ROP of silicon-bridged [1]ferrocenophanes in the presence of various transition-metal complexes (eg, PtII , Pt0 , RhI ,
PdII ) has been developed (164). This route, which takes place in solution at room
temperature, is much milder than, and doesnt have the same stringent monomer
purity requirements as, anionic ROP. Furthermore, molecular weight control is
possible through the use of Si H containing capping agents such as (C2 H5 )3 SiH,
and access to block and graft copolymers and star polymers is possible (164,165).
Monomer Synthesis. Sila[1]ferrocenophane monomers such as (43) are
readily available on a substantial laboratory scale (>100 g) from the reaction
of dilithioferrocene tetramethylethylenediamine (fcLi2 TMEDA) with the appropriate dichloroorganosilane (166). Spirocyclic sila[1]ferrocenophanes such as (45)
and (46) are also easily synthesized (167). Sila[1]ferrocenophane monomers with
alkoxy, aryloxy, and amino substituents at silicon are readily accessible through
reaction of dichlorosila[1]ferrocenophane with the appropriate alcohol, phenol or
amine in the presence of base (168).

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Other Polyferrocenes
The ROP route has been extended to the synthesis of other polymers from [1]ferrocenophane precursors. Polyferrocenylgermanes (47) were rst reported in 1993
and have been well-characterized and possess quite similar thermal transition
behavior, morphology, and electrochemical behavior to the analogous polyferrocenylsilanes (169). Poly(ferrocenylsilane-ferrocenylgermane) random copolymers
(48) have also been prepared via the thermal polymerization of mixtures of the
respective monomers (169).

Polyferrocenylphosphines (49) (and the corresponding phosphine suldes)

are also accessible via the thermal ROP of phosphorus-bridged [1]ferrocenophanes
(170). Polymers of this type have been previously prepared by condensation routes
and the catalytic potential of some of their transition-metal derivatives has already been noted. In addition, the rst sulfur-bridged [1]ferrocenophanes have
been prepared and polymerized to give polyferrocenylsuldes, (eg, 50) (171).

Hydrocarbon-bridged [2]-ferrocenophanes (51) possess strained ring-tilted

structures (tilt-angles = ca 21 ) and these species have been found to yield polyferrocenylethylenes (52) via ROP at 250300 C (eq. 33) (172). As a consequence
of the presence of a more insulating bridge, these polymers show much smaller
interactions between the iron atoms compared to polyferrocenylsilanes.

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(33)
Analogous hydrocarbon-bridged [2]ruthenocenophanes (tilt angles = ca
2930 ) undergo thermal ROP to yield poly(ruthenocenylethylenes) (172).
These materials exhibit signicantly different electrochemistry from their iron
analogues.
In early 1992, it was reported that [3]trithiaferrocenophanes, which are essentially unstrained, function as precursors to poly(ferrocenylene persuldes) via
a novel atom abstraction polymerization route (eq. 34) (173). Thus, reaction of
[3]-trithiaferrocenophanes (53) with P(C4 H9 )3 led to the formation of the phosphine sulde S P(C4 H9 )3 and the polymers (54).

(34)
The presence of a butyl substituent on the cyclopentadienyl ring is necessary
for the polymer to be soluble. The molecular weight (M w ) of (54) (R = n-C4 H9 ) was
determined to be 40,000 by gel permeation chromatography (gpc). The [3]ferrocenophanes (53) (R = H) and (53) (R = n-C4 H9 ) can be copolymerized to give
soluble copolymers with M w = 25,000.
Poly(ferrocenylene persuldes) possess a range of novel properties (173
175). They are photosensitive and the S S bonds can be reversibly reductively
cleaved with Li[B(C2 H5 )3 H] and then regenerated upon oxidation with I2 . Their
electrochemical behavior is similar to that detected for polyferrocenylsilanes except that the interaction between the iron sites appears to be even greater. The
atom abstraction route using P(t C4 H9 )3 as a desulfurization agent has also been
extended to the preparation of other poly(ferrocenylene persuldes) with t-butyl
substituents and also high molecular weight (M w = 50,0001,000,000) network
polymers by the use of [3]ferrocenophanes with two trisuldo bridges as monomers
(174).

Face-to-Face Metallocene Polymers

The development of rigid-rod metallocene polymers with a multistacked structure
using condensation routes has been reported (176180). This involved treatment
of the ferrocene monomers (55) with FeCl2 and Na[N(Si(CH3 )3 )2 )] and this yielded
purple polymers (56) with molecular weights up to M n = 18,000, although higher

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molecular components were also present (eq. 35). Mixed metal copolymers containing Ni and Fe whose soluble fractions were of low molecular weight (M n < 3000)
were also reported by using Ni(acac)2 instead of FeCl2 (176). The electrical and
magnetic properties of these novel polymers and copolymers are clearly worthy of
investigation. Interestingly, structural work on well-dened oligomers suggests
that the stacked metallocene units in the polymer form a helical structure (180).

(35)

Coordination Polymers
In the past, attempts to prepare coordination polymers have been hindered by the
insolubility and consequent intractability of the products. These problems arise
from the inherent skeletal rigidity of these materials, and the introduction of solubilizing or exibilizing groups either in the polymer backbone or side-group structure is necessary for useful products to be obtained. Such modication has yielded
a range of interesting and well-characterized materials with intriguing properties. For example, novel liquid crystalline polymers (57) containing paramagnetic
CuII centers have been prepared (181) and soluble, luminescent silver-containing
polymers (58) have been reported (182).

In addition, well-characterized lanthanide containing polymers (59), which

possess polyelectrolyte behavior and exhibit interesting photophysical properties,
have been reported (183). The tetradentate Schiff-Base ligands greatly stabilize the lanthanide ions in solution and allow for efcient energy transfer to the

Vol. 3

INORGANIC POLYMERS

57

lanthanide centers. Several of the polymers are soluble in polar organic solvents
such as DMSO, and molecular weights (M n ) up to 1.8 104 have been established.
The polymer (59) (Ln = Eu or Eu/Y) is an interesting candidate for luminescent
and lasing applications (184). Similar polymers containing cerium and zirconium
in the main chain have also been prepared and these possess M n values up to
3 104 (185). Films of these polymers have conductivities of 10 7 S/cm which
increase to 10 3 S/cm upon I2 doping (186).

Phthalocyanine-based polymers, such as the shish-kebab polymers (60),

are also of considerable interest and signicant electrical conductivities of up to
ca 0.1 S/cm have been detected for chemically or electrochemically doped materials (187,188). If exible organic substituents are present on the periphery of the
phthalocyanine ring, these materials can also be soluble (at least low molecular
weight fractions).

Well-dened and readily soluble ruthenium coordination polymers (61) have

been synthesized through the reaction of a bisbidentate ligand and a metal center
that already possesses one bidentate ligand (189191). In these complexes, the
random stereospecicity at the ruthenium centers results in a ribbon-like conformation of the polymers with the extension of the chain dependent upon the
substituent R. The RuII centers appear to behave independently and the polymers appear to be stable against heat and uv irradiation. They have molecular
weights on the order of M w = 40,00050,000.

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A similar strategy applied to the reaction of a bistridentate monomer with an

appropriate ruthenium compound gives rise to the rod-like polymers (62), which
are soluble due to the n-hexyl substituents (192,193). These polymers display a
pronounced polyelectrolytic effect in salt-free dimethylacetamide.

Polythiophene-metal complex hybrid polymers such as (63) and (64)

have been explored (194,195). The polythiophene-cobalt salen hybrid (63)
participates in the electrocatalytic reduction of oxygen and is highly conducting in nature. Polymers such as (64) have also been shown to be conducting. A variety of related structures have been prepared and similar strategies have also resulted in the preparation of polymeric metallorotaxanes
(196).

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The generation of dendrimeric coordination polymers has also been an area of

signicant activity. Imaginative routes to novel Ru- or Pt-polypyridyl systems (eg,
65) (197) have been reported and many other ligand systems have been exploited
(117,118,198201). These materials are of interest with respect to their photophysical and electrochemical properties and possibly their catalytic behavior.

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Rigid-Rod Organometallic Polymers

Macromolecules with backbones that possess conjugated C C units and
transition-metal atoms, termed polymetallaynes, represent some of the
best-characterized examples of transition-metal-based polymers prepared to
date (202).
The rst polymetallaynes contained nickel, palladium, or platinum atoms
in the main chain and were isolated in 1977 as yellow, lm forming materials
(203205). These were prepared by efcient copper halide-catalyzed coupling processes (eg, eq. 36) and possessed estimated molecular weights (M w ) from 13,000
to 120,000.

(36)
There has been an important expansion in this area which has yielded a
range of new rigid-rod materials via the creative use of a variety of new and
well-dened polycondensation strategies. For example, a new route to the polyplatinynes (66) that involved the reaction of trans-PtCl2 (PR3 )2 complexes with
bis(trimethylstannyl)diynes (eq. 37) has been reported (206). These rigid-rod polymers possessed estimated weight-average molecular weights up to ca 100,000 according to gpc measurements.

(37)
This synthetic procedure can be extended to allow the incorporation of other
transition elements into the polymer main chain such as iron (to give 67) by using
FeCl2 [(C2 H5 )2 PCH2 CH2 P(C2 H5 )2 ]2 as the transition-metal-containing reactant
(207). In addition, condensation routes to organonickel polymers (68), have been
devised (208,209) and interesting organocobalt (210) and organozirconium (211)
polymers containing metallacyclopentadiene moieties in the main chain have been
reported.

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61

In another interesting synthetic development, it was shown that a range

of rhodium-containing polymetallynes (69) are accessible via the reaction of the
unsubstituted diynes with Rh(PR3 )4 CH3 in a reaction that involves reductive
elimination of methane and the loss of a phosphine ligand (eq. 38) (212). In
the case where trimethylphosphine ligands are attached to rhodium, the polymers are insoluble but the tri(n-butyl)phosphine analogues are soluble and yield
free-standing solvent-cast lms from THF.

(38)
Over the past 15 years the physical properties of polymetallaynes have received continued attention because of their novel rigid-rod structures and their
conjugated backbones (213222). Thus, polyplatinynes form ordered, liquid crystalline mesophases in solvents in which they are soluble such as trichloroethylene (213), and these materials also possess novel, third-order nonlinear optical
properties (214) that are of interest for electrooptic device applications. Optical

absorption and photoluminescence spectroscopic studies and extended Huckel

calculations have shown that polymetallaynes possess a delocalized polymer backbone whose electronic structure is modied by the nature of the transition metal,
coligands, and the unsaturated hydrocarbon spacer (215217). For example, optical band gaps for a series of polyplatinynes with platinum centers joined by
-conjugated acetylide-arene linkages of varying length have been measured to
be in the range of 2.53.1 eV, which is lower than for model complexes and is
consistent with conjugation through the metal centers (216).
Other developments in the area of rigid-rod transition-metal-based polymers
include the synthesis of a range of thermotropic liquid crystalline organocobalt
polymers (eg, 70) in which the metal is bound to skeletal cyclobutadiene units (eq.
39) (223).

(39)
In addition, the preparation and characterization of novel lyotropic liquid
crystalline aramides (71) with complexed chromium(tricarbonyl) units have been

62

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Vol. 3

reported (224). These materials are soluble in organic solvents, which leads to potential processing advantages for the uncomplexed organic polymer as the Cr(CO)3
groups can be easily added and removed and poly(p-phenyleneterephthalamide)
is only soluble in concentrated sulfuric acid (224,225). Work on the coordination of
transition-metal fragments to -hydrocarbon units can be found in Reference 226.

BIBLIOGRAPHY
Inorganic Polymers in EPST 1st ed., Vol. 8, pp. 664691, by D. L. Venezky, U.S. Naval
Research Laboratory; Inorganic Polymers in EPSE 2nd ed., Vol. 8, pp. 138147, by A.
Rheingold, University of Delaware.
1. J. E. Mark, H. R. Allcock, and R. West, Inorganic Polymers, Prentice Hall, Englewood
Cliffs, N.J., 1992; I. Manners, Angew. Chem. Int. Ed. Engl. 35, 1603 (1996); R. D.
Archer, Inorganic and Organometallic Polymers, Wiley-VCH, New York, 2001.
2. R. H. Neilson and co-workers, ACS Symp. Ser. 572, 232 (1994), and references therein.
3. P. Wisian-Neilson, ACS Symp. Ser. 572, 246 (1994).
4. R. de Jaeger and M. Gleria, Prog. Polym. Sci. 23, 179 (1998), and references therein.
5. H. R. Allcock and R. L. Kugel, J. Am. Chem. Soc. 87, 4216 (1965).
6. H. R. Allcock, J. Inorg. Organomet. Polym. 2, 197 (1992).
7. H. R. Allcock, Chem. Mater. 6, 1476 (1994).
8. H. R. Allcock, Adv. Mater. 6, 106 (1994).
9. H. R. Allcock and C. Kim, Macromolecules 22, 2596 (1989).
10. H. R. Allcock and C. Kim, Macromolecules 24, 2846 (1991).
11. H. R. Allcock, A. A. Dembek, and E. H. Klingenberg, Macromolecules 24, 5208 (1991).
12. H. R. Allcock and C. G. Cameron, Macromolecules 27, 3131 (1994).
13. G. Facchin and co-workers, J. Inorg. Organomet. Polym. 1, 389 (1991).
14. D. C. Ngo, J. S. Rutt, and H. R. Allcock, J. Am. Chem. Soc. 113, 5075 (1991).
15. H. R. Allcock and co-workers, Macromolecules 27, 7556 (1994).
16. R. H. Neilson and P. Wisian-Neilson, Chem. Rev. 88, 541 (1988); C. H. Walker, J. V.
St. John, and P. Wisian-Neilson, J. Am. Chem. Soc. 123, 3846 (2001).
17. R. A. Montague and K. Matyjaszewski, J. Am. Chem. Soc. 112, 6721 (1990).
18. K. Matyjaszewski, J. Inorg. Organomet. Polym. 2, 5 (1992); K. Matyjaszewski and
co-workers, J. Polym. Sci., Part A: Polym. Chem. 30, 813 (1992); K. Matyjaszewski and
co-workers, Polymer 35, 5005 (1994); U. Franz, O. Nuyken, and K. Matyjaszewski,
Macromolecules 26, 3723 (1993).
19. G. DHalluin and co-workers, Macromolecules 25, 1254 (1992).
20. C. H. Honeyman and co-workers, J. Am. Chem. Soc. 117, 7035 (1995).
21. H. R. Allcock and co-workers, Macromolecules 29, 7740 (1996).
22. J. M. Nelson and H. R. Allcock, Macromolecules 30, 1854 (1997).
23. H. R. Allcock and co-workers, Macromolecules 30, 2213 (1997).
24. H. R. Allcock and co-workers, Macromolecules 33, 3999 (2000).

Vol. 3
25.
26.
27.
28.
29.
30.

31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.

INORGANIC POLYMERS

63

H. R. Allcock and co-workers, Inorg. Chem. 38, 280 (1999).

E. Niecke and W. Bitter, Inorg. Nucl. Chem. Lett. 9, 127 (1973).
R. West, J. Organomet. Chem. 300, 327 (1986).
R. D. Miller and J. Michl, Chem. Rev. 89, 1359 (1989).
K. Matyjaszewski, J. Inorg. Organomet. Polym. 1, 463 (1991).
H. Teramae and K. Takeda, J. Am. Chem. Soc. 111, 1281 (1989); J. T. Nelson and W.
J. Pietro, J. Phys. Chem. 92, 1365 (1988); A. Savin and co-workers, Angew. Chem.
Int. Ed. Engl. 31, 187 (1992).
P. Trefonas, Encycl. Polym. Sci. Eng. 13, 162 (1987).
H. Tachibana and co-workers, Phys, Rev. B 47, 4363 (1993).
K. S. Madiyasni, R. West, and L. D. David, J. Am. Ceram. Soc. 61, 504 (1978).
C. Aitken, J. F. Harrod, and E. Samuel, J. Organomet. Chem. 279, C11 (1985); C. T.
Aitken, J. F. Harrod, and E. Samuel, J. Am. Chem. Soc. 108, 4059 (1986).
T. D. Tilley, Acc. Chem. Res. 26, 22 (1993), and references therein.
M. Scarlete and co-workers, Chem. Mater. 6, 977 (1994).
Y.-L. Hsiao and R. M. Waymouth, J. Am. Chem. Soc. 116, 9779 (1994).
M. Cypryk, Y. Gupta, and K. Matyjaszewski, J. Am. Chem. Soc. 113, 1046 (1991); E.
Fossum and K. Matyjaszewski, Macromolecules 28, 1618 (1995).
K. Sakamoto and co-workers, J. Am. Chem. Soc. 111, 7641 (1989).
H. Sakurai and co-workers, ACS Symp. Ser. 572, 8 (1994).
T. Sanji, F. Kitayama, and H. Sakurai, Macromolecules 32, 5718 (1999).
H. Suzuki and co-workers, Adv. Mater. 5, 743 (1993).
Y. Wang, R. West, and C. H. Yuan, J. Am. Chem. Soc. 115, 3844 (1993).
P. Trefonas and R. West, J. Polym. Sci., Polym. Chem. 23, 2099 (1985).
R. D. Miller and R. Sooriyakumaran, J. Polym. Sci., Part A: Polym. Chem. 25, 111
(1987).
S. M. Katz, J. A. Reichl, and D. H. Berry, J. Am. Chem. Soc. 120, 9844 (1998).
M. Okano and co-workers, Electrochim. Acta 44, 659 (1998).
V. Y. Lu and T. D. Tilley, Macromolecules 33, 2403 (2000).
T. Hayashi and co-workers, Chem. Lett. 647 (1992).
T. Kodaira and co-workers, Adv. Mater. 7, 917 (1995); J.-C. Baumert and co-workers,
Appl. Phys. Lett. 53, 1147 (1988).
T. Imori and T. D. Tilley, Chem. Commun. 1607 (1993).
T. Imori and co-workers, J. Am. Chem. Soc. 117, 9931 (1995).
K. Mochida and H. Chiba, J. Organomet. Chem. 473, 45 (1994).
C. Aitken and co-workers, J. Organomet. Chem. 349, 285 (1988).
M. Okano, T. Toriumi, and H. Hamano, Electrochim. Acta 44, 3475 (1999).
J. A. Reichl and co-workers, J. Am. Chem. Soc. 118, 9430 (1996).
V. Lu and T. D. Tilley, Macromolecules 29, 5763 (1996).
J. R. Babcock and L. R. Sita, J. Am. Chem. Soc. 118, 12481 (1996).
K. Mochida and co-workers, J. Organomet. Chem. 542, 75 (1997).
H. Ban, K. Deguchi, and A. Tanaka, J. Appl. Polym. Sci. 37, 1589 (1989).
M. Abkowitz and M. Stolka, Solid State Commun. 78, 269 (1991).
M. Abkowitz and M. Stolka, J. Non-Cryst. Solids 114, 342 (1989).
K. Mochida and co-workers, Appl. Organomet. Chem. 11, 949 (1997).
Y. Chujo, N. Takizawa, and T. Sakurai, Chem. Commun. 227 (1994).
Y. Chujo, ACS Symp. Ser. 572, 398 (1994).
R. T. Paine and C. K. Narula, Chem. Rev. 90, 73 (1990); R. T. Paine, J. Inorg.
Organomet. Polym. 2, 183 (1992).
R. T. Paine and L. G. Sneddon, ACS Symp. Ser. 572, 358 (1994).
P. J. Fazen and co-workers, Chem. Mater. 2, 96 (1990).
P. J. Fazen and co-workers, Chem. Mater. 7, 1942 (1995).

64
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.

108.
109.
110.
111.
112.
113.
114.
115.
116.
117.

INORGANIC POLYMERS

Vol. 3

Y. Chujo and co-workers, Macromolecules 24, 345 (1991).

Y. Chujo and co-workers, Macromolecules 25, 33 (1992).
Y. Chujo, I. Tomita, and T. Saegusa, Macromolecules 23, 687 (1990).
N. Matsumi, K. Naka, and Y. Chujo, J. Am. Chem. Soc. 120, 5112 (1998).
N. Matsumi, M. Miyata, and Y. Chujo, Macromolecules 32, 4467 (1999).
Y. Sasaki and Y. Chujo, Polym. Prepr. Jpn. 45, 214 (1996).
N. Matsumi and Y. Chujo, Macromolecules 31, 3802 (1998).
Y. Chujo and co-workers, Macromolecules 25, 27 (1992).
Y. Chujo, I. Tomita, and T. Saegusa, Macromolecules 27, 6714 (1994).
N. Matsumi, K. Naka, and Y. Chujo, Macromolecules 31, 8047 (1998).
N. Matsumi, T. Umeyama, and Y. Chujo, Macromolecules 33, 3956 (2000).
N. Matsumi and co-workers, Macromolecules 31, 3155 (1998).
N. Matsumi, K. Kotera, and Y. Chujo, Macromolecules 33, 2801 (2000).
N. Matsumi, K. Naka, and Y. Chujo, J. Am. Chem. Soc. 120, 10776 (1998).
H. Dorn and co-workers, Angew. Chem. Int. Ed. 38, 3321 (1999).
R. I. Wagner and F. F. Caserio Jr., J. Inorg. Nucl. Chem. 11, 259 (1959).
A. B. Burg, J. Inorg. Nucl. Chem. 11, 258 (1959).
H. Dorn and co-workers, J. Am. Chem. Soc. 122, 6669 (2000).
I. Manners and co-workers, J. Am. Chem. Soc. 111, 5478 (1989).
H. R. Allcock and co-workers, Macromolecules 24, 2024 (1991).
H. R. Allcock and co-workers, Inorg. Chem. 32, 5088 (1993).
H. R. Allcock, S. M. Coley, and C. T. Morrissey, Macromolecules 27, 2904 (1994).
I. Manners, Coord. Chem. Rev. 137, 109 (1994).
M. M. Labes, P. Love, and L. F. Nichols, Chem. Rev. 79, 1 (1979).
J. A. Dodge and co-workers, J. Am. Chem. Soc. 112, 1268 (1990).
H. R. Allcock, J. A. Dodge, and I. Manners, Macromolecules 26, 11 (1993).
M. Liang and I. Manners, J. Am. Chem. Soc. 113, 4044 (1991).
M. Liang and I. Manners, Makromol. Chem., Rapid Commun. 12, 613 (1991).
J. C. van de Grampel, Rev. Inorg. Chem. 3, 1 (1981); J. C. van de Grampel, Coord.
Chem. Rev. 112, 247 (1992).
A. R. McWilliams and co-workers, J. Am. Chem. Soc. 122, 8848 (2000).
Y. Ni and co-workers, Angew. Chem. Int. Ed. Engl. 34, 998 (1995).
Y. Ni and co-workers, Macromolecules 25, 7119 (1992).
Y. Ni and co-workers, Macromolecules 29, 3401 (1996).
M. N. Nobis and co-workers, Macromolecules 33, 7707 (2000).
R. Jaeger and co-workers, Macromolecules 28, 539 (1995).
Z. Pang and co-workers, Adv. Mater. 8, 768 (1996).
V. Chunechom and co-workers, Angew. Chem. Int. Ed. 37, 1928 (1998).
T. Chivers and co-workers, in R. Steudel, ed., Studies in Inorganic Chemistry, Vol. 14:
The Chemistry of Inorganic Ring Systems, Elsevier, Amsterdam, Netherlands, 1992,
p. 271.
F. Seel and G. Simon, Angew. Chem. 72, 709 (1960); G. W. Parshall, R. Cramer, and
R. E. Foster, Inorg. Chem. 1, 677 (1962).
A. K. Roy, J. Am. Chem. Soc. 114, 1530 (1992).
A. K. Roy and co-workers, J. Am. Chem. Soc. 115, 2604 (1993).
C. U. Pittman Jr. and co-workers, Macromolecules 3, 746 (1970).
W. J. Patterson, S. P. McManus, and C. U. Pittman Jr., J. Polym. Sci. Part A-1 12, 837
(1974).
K. Gonsalves, L. Zhan-ru, and M. D. Rausch, J. Am. Chem. Soc. 106, 3862 (1984).
M. E. Wright, and M. S. Sigman, Macromolecules 25, 6055 (1992).
M. E. Wright and co-workers, Macromolecules 27, 3016 (1994).
P. Nguyen, P. Gomez-Elipe, and I. Manners, Chem. Rev. 99, 1515 (1999).
M. A. Hearshaw and J. R. Moss, Chem. Commun. 1 (1999).

Vol. 3
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
160.
161.
162.
163.
164.
165.
166.
167.

INORGANIC POLYMERS

65

C. Gorman, Adv. Mater. 10, 295 (1998).

B. Alonso and co-workers, Chem. Commun. 2575 (1994).
I. Cuadrado and co-workers, Organometallics 15, 5278 (1996).
J.-L. Fillaut, J. Linares, and D. Astruc, Angew. Chem. Int. Ed. Engl. 33, 2460 (1994).
C. Valerio and co-workers, J. Am. Chem. Soc. 119, 2588 (1997).
I. Cuadrado and co-workers, J. Am. Chem. Soc. 119, 7613 (1997).
U. T. Mueller-Westerhoff, Angew. Chem. Int. Ed. Engl. 25, 702 (1986).
W. H. Morrison Jr. and D. N. Hendrickson, Inorg. Chem. 14, 2331 (1975); J. A. Kramer
and D. N. Hendrickson, Inorg. Chem. 19, 3330 (1980).
E. W. Neuse and H. Rosenberg, J. Macromol. Sci., C: Rev. Macromol. Chem. 4, 1 (1970).
R. Bayer, T. Pohlmann, and O. Nuyken, Makromol. Chem., Rapid Commun. 14, 359
(1993); C. E. Stanton and co-workers, Macromolecules 28, 8713 (1995).
C. U. Pittman Jr. and Y. Sasaki, Chem. Lett. 383 (1975).
N. Bilow, A. L. Landis, and H. Rosenberg, J. Polym. Sci. Part A-1 7, 2719 (1969).
E. W. Neuse and L. Bednarik, Macromolecules 12, 187 (1979).
T. Yamamoto and co-workers, Inorg. Chim. Acta 73, 75 (1983).
D. A. Foucher, B.-Z. Tang, and I. Manners, J. Am. Chem. Soc. 114, 6246 (1992).
I. Manners, Chem. Commun. 857 (1999).
D. A. Foucher and co-workers, Angew. Chem. Int. Ed. Engl. 32, 1709 (1993).
R. Rulkens and co-workers, J. Am. Chem. Soc. 118, 12683 (1996).
M. Hmyene and co-workers, Adv. Mater. 6, 564 (1994).
J. K. Pudelski and co-workers, Macromolecules 29, 1894 (1996).
L. I. Espada and co-workers, J. Inorg. Organomet. Polym. 10, 169 (2000).
R. Resendes and co-workers, Adv. Mater. 12, 327 (2000).
I. Manners, Pure Appl. Chem. 71, 1471 (1999).
J. Rasburn and co-workers, Chem. Mater. 7, 871 (1995); S. Barlow and co-workers,
J. Am. Chem. Soc. 118, 7578 (1996).
V. S. Papkov and co-workers, Macromolecules 33, 7107 (2000).
K. Kulbaba and I. Manners, Macromol. Rapid Commun., 22, 711 (2001).
I. Manners, Adv. Organomet. Chem. 37, 131 (1995).
R. Petersen and co-workers, Chem. Mater. 7, 2045 (1995).
M. J. MacLachlan and co-workers, Adv. Mater. 10, 144 (1998).
M. J. MacLachlan and co-workers, J. Am. Chem. Soc. 122, 3878 (2000).
M. J. MacLachlan and co-workers, Science 287, 1460 (2000).
M. J. MacLachlan, A. J. Lough, and I. Manners, Macromolecules 29, 8562 (1996).
J. A. Massey and co-workers, J. Polym. Sci. Part B: Polym. Phys. 38, 3032 (2000).
K. N. Power-Billard and I. Manners, Macromolecules 33, 26 (2000).

F. Jakle,
Z. Wang, and I. Manners, Macromol. Rapid Commun. 21, 1291 (2000).
M. Ginzburg and co-workers, Langmuir 16, 9609 (2000).
E. Fossum and co-workers, Macromolecules 28, 401 (1995).
R. Rulkens and co-workers, Macromolecules 30, 8165 (1997).
J. A. Massey and co-workers, Adv. Mater. 10, 1559 (1998).
J. A. Massey and co-workers, J. Am. Chem. Soc. 123, 3147 (2001).
I. Manners, Can. J. Chem. 76, 371 (1998).
J. K. Pudelski and co-workers, Macromolecules 28, 7301 (1995).
R. Rulkens, Y. Ni, and I. Manners, J. Am. Chem. Soc. 116, 12121 (1994).
Y. Ni, R. Rulkens, and I. Manners, J. Am. Chem. Soc. 118, 4102 (1996).
J. A. Massey and co-workers, J. Am. Chem. Soc. 122, 11577 (2000).
J. A. Massey and co-workers, J. Am. Chem. Soc. 120, 9533 (1998).
P. Gomez-Elipe and co-workers, J. Am. Chem. Soc. 120, 8348 (1998).
R. Resendes and co-workers, Macromolecules 33, 8 (2000).
Y. Ni and co-workers, J. Chem. Ed. 75, 766 (1998).
M. J. MacLachlan and co-workers, Organometallics 17, 1873 (1998).

66
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
207.
208.
209.
210.
211.
212.
213.
214.
215.

INORGANIC POLYMERS

Vol. 3

P. Nguyen and co-workers, Macromolecules 31, 5977 (1998).

T. J. Peckham and co-workers, Macromolecules 29, 2396 (1996).
T. J. Peckham and co-workers, Macromolecules 32, 2830 (1999).
R. Rulkens and co-workers, J. Am. Chem. Soc. 119, 10976 (1997).
J. M. Nelson and co-workers, Chem. Eur. J. 3, 573 (1997).
P. F. Brandt and T. B. Rauchfuss, J. Am. Chem. Soc. 114, 1926 (1992).
C. P. Galloway and T. B. Rauchfuss, Angew. Chem. Int. Ed. Engl. 32, 1319 (1993).
D. L. Compton and T. B. Rauchfuss, Organometallics 13, 4367 (1994); D. L. Compton
and co-workers, Chem. Mater. 7, 2342 (1995).
H. M. Nugent, M. Rosenblum, and P. Klemarczyk, J. Am. Chem. Soc. 115, 3848 (1993).
M. Rosenblum, Adv. Mater. 6, 159 (1994).
M. Rosenblum and co-workers, Macromolecules 28, 6330 (1995).
R. Arnold, S. A. Matchett, and M. Rosenblum, Organometallics 7, 2261 (1988); B. M.
Foxman and co-workers, Organometallics 12, 4805 (1993).
B. M. Foxman, D. A. Gronbeck, and M. Rosenblum, J. Organomet. Chem. 413, 287
(1991).
M. Marcos, L. Oriol, and J. L. Serrano, Macromolecules 25, 5362 (1992).
D. Perreault and co-workers, Inorg. Chem. 31, 3688 (1992).
H. Chen and R. D. Archer, Macromolecules 28, 1609 (1995).
H. Chen and R. D. Archer, Macromolecules 29, 1957 (1996).
H. Chen, J. A. Cronin, and R. D. Archer, Macromolecules 27, 2174 (1994).
J. A. Cronin, S. M. Palmer, and R. D. Archer, Inorg. Chim. Acta 251, 81 (1996).
M. Hanack and M. Lang, Adv. Mater. 6, 819 (1994).
T. J. Marks, Angew. Chem. Int. Ed. Engl. 29, 857 (1990).
R. Knapp, A. Schott, and M. Rehahn, Macromolecules 29, 478 (1996).
S. Kelch and M. Rehahn, Macromolecules 30, 6185 (1997).
S. Kelch and M. Rehahn, Macromolecules 31, 4102 (1998).
S. Kelch and M. Rehahn, Chem. Commun. 1123 (1999).
S. Kelch and M. Rehahn, Macromolecules 32, 5818 (1999).
R. P. Kingsborough and T. M. Swager, Chem. Mater. 12, 872 (2000).
S. S. Zhu, R. P. Kingsborough, and T. M. Swager, J. Mater. Chem. 9, 2123 (1999).
J. Buey and T. M. Swager, Angew. Chem. Int. Ed. 39, 608 (2000).
E. C. Constable and P. Harverson, Inorg. Chim. Acta 252, 9 (1996).
S. Achar and R. J. Puddephatt, Angew. Chem. Int. Ed. Engl. 33, 847 (1994).
S. Achar and R. J. Puddephatt, Chem. Commun. 1895 (1994).
S. Serroni and co-workers, Angew. Chem. Int. Ed. Engl. 31, 1493 (1992).
G. R. Newkome and co-workers, Chem. Commun. 925 (1993).
M. H. Chisholm, Angew. Chem. Int. Ed. Engl. 30, 673 (1991).
K. Sonogashira, S. Takahashi, and N. Hagihara, Macromolecules 10, 879 (1977).
S. Takahashi and co-workers, Macromolecules 11, 1063 (1978).
N. Hagihara, K. Sonogashira, and S. Takahashi, Adv. Polym. Sci. 41, 149 (1981).
S. J. Davies and co-workers, Chem. Commun. 187 (1991).
B. F. G. Johnson and co-workers, J. Organomet. Chem. 409, C12 (1991).
K. C. Sturge and co-workers, Organometallics 11, 3056 (1992).
X. A. Guo and co-workers, Macromolecules 27, 7825 (1994).
H. Nishihara and co-workers, Adv. Mater. 5, 752 (1993); I. Tomita, A. Nishio, and T.
Endo, Macromolecules 27, 7009 (1994).
S. S. H. Mao and T. D. Tilley, J. Am. Chem. Soc. 117, 5365 (1995).
H. B. Fyfe and co-workers, Chem. Commun. 188 (1991).
A. Abe, N. Kimura, and S. Tabata, Macromolecules 24, 6238 (1991).
C. C. Frazier and co-workers, Polymer 28, 553 (1987).
J. Lewis and co-workers, J. Organomet. Chem. 425, 165 (1992).

Vol. 3

INORGANIC POLYMERS

67

216.
217.
218.
219.
220.
221.
222.
223.
224.
225.

M. S. Khan and co-workers, J. Mater. Chem. 4, 1227 (1994).

G. Frapper and M. Kertesz, Inorg. Chem. 32, 732 (1993).
W. J. Blau and co-workers, J. Mater. Chem. 1, 245 (1991).
A. E. Dray and co-workers, Synthetic Metals 4143, 871 (1991).
C. W. Faulkner and co-workers, J. Organomet. Chem. 482, 139 (1994).
K. A. Bunten and A. K. Kakkar, J. Mater. Chem. 5, 2041 (1995).
G. Jia and co-workers, Organometallics 12, 263 (1993).
M. Altmann and co-workers, Adv. Mater. 7, 726 (1995).
A. A. Dembek, R. R. Burch, and A. E. Feiring, J. Am. Chem. Soc. 115, 2087 (1993).
D. Tanner, J. A. Fitzgerald, and B. R. Phillips, Angew. Chem. Int. Ed. Engl. Adv. Mater.
28, 649 (1989).
226. A. A. Dembek, P. J. Fagan, and M. Marsi, Macromolecules 26, 2992 (1993); A. S.
Abd-El-Aziz and C. R. de Denus, Chem. Commun. 663 (1994).

SARA C. BOURKE
IAN MANNERS
University of Toronto

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