inorganic and organometallic polymers

Inorganic and organometallic polymers

Kevin J. T. Noonan and Derek P. Gates*DOI: 10.1039/b612872f

The synthesis of macromolecules composed partially or entirely of inor-ganic elements in the main chain is an area of widespread interest. Thisreport summarizes the many advances that were made in the area ofinorganic polymer science in 2006.

Highlights

Major accomplishments in the synthesis of inorganic polymers include: the observa-

tion of molecular weight doubling when polysilanes are synthesized in chiral

solvents, the synthesis of P–H polyphosphazenes, the development of polyphos-

phole-based sensors, the ring-opening polymerization of phosphirenes, the living

anionic polymerization of PQC bonds, the ring-opening polymerization of [1]sila-

trochrocenophanes, and the development of palladium-containing polymers as

supramolecular cruciforms.

1 Introduction

The synthesis of macromolecules composed partially or entirely of inorganic

elements in the main chain is an area of widespread interest. A major challenge

facing researchers in this area is the development of general synthetic methods to

link inorganic elements into long chains. Despite these hurdles, researchers are

motivated to develop polymers containing main group elements or transition metals

due to their novel properties and possible applications.

In this article, the 2006 literature in the area of inorganic and organometallic

polymers shall be surveyed. This report complements previous articles in this series,1

and is divided into eight sections beginning with this introductory part. The next

subsection will give an overview of recent books, reviews and highlight articles that

have been published in the area. This is followed by three subsections devoted to the

well-established polysiloxanes (silicones), polysilanes, and polyphosphazenes. This is

followed by a summary of advances in the development of new types of macro-

molecules composed partially or entirely of main group elements. A section will then

be devoted to the growing field of ferrocene and related organometallic polymers.

The final section will highlight progress in the synthesis of macromolecules contain-

ing transition metals within the main chain.

In this review, emphasis will be placed on synthetic advances in the development

of linear macromolecules containing main group elements or transition metals

within the main chain.

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver,Canada BC V6T 1Z1

Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407–427 | 407

This journal is �c The Royal Society of Chemistry 2007

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http://pubs.rsc.org/en/journals/journal/IC?issueid=IC007103

2 Books and reviews of inorganic polymer science

A book entitled Metal-Containing and Metallosupramolecular Polymers and Materi-

als has been published in 2006 as part of the ACS symposium series.2 The editors,

Schubert, Newkome, and Manners have assembled a wonderful collection of articles

from a variety of leading researchers in the field. An excellent monograph entitled

Frontiers in Transition Metal-Containing Polymers has appeared which features

chapters written by leaders in the field.3 A special issue of Current Organic Chemistry

has appeared on organophosphorus chemistry in which phosphorus-containing

macrocycles and dendrimers are described.4

An interesting review of the literature on the Pt content in commercial silicones

and its implications for biomedical applications has appeared.5 The use of acyclic

diene metathesis (ADMET) to prepare silicon–carbon hybrid materials has been

highlighted.6 Divinylarene-silylene copolymers have been reviewed in a Chemical

Communications feature article.7 A review of Wurtz-type coupling to synthesize

polysilanes in high yields has been compiled by Jones and Holder.8 Weak non

covalent Si� � �F–C interactions of fluorosilane polymers have been highlighted.9

Several reviews of phosphazene macromolecules have appeared on topics ranging

from ion conductivity,10 the use of polyphosphazenes as hydrophobic surfaces,11 to

recent developments of metal-containing phosphazene macromolecules.12

New directions in main group polymers have been reviewed fairly extensively in

2006. A comprehensive review of p-conjugated phosphorus-containing materials by

Baumgartner and Reau has been published.13 A review of the synthesis and

properties of bithiophenes containing heteroatoms has appeared.14 Jakle has high-

lighted the incorporation of Lewis acidic boron centres into macromolecules.15 Two

reviews highlighting recent advances in dehydrocoupling as a route to polymers

possessing inorganic elements have been published.16,17

Advances in ring opening polymerization (ROP) and supramolecular polymer self

assembly has been highlighted.18 An overview of the recent advances in transition

metal containing conjugated polymers has appeared.19 Conjugated organometallic

polymer networks and metal-containing supramolecular architectures have been

reviewed.20,21 Organometallic structures p bonded to quinonoids forming coordina-

tion networks has been highlighted.22,23 Using metallo-supramolecular initiators for

controlled polymerization has been reviewed.24 An article on organometallic poly-

mer nanostructures has appeared.25 Reviews on phosphorus-, metal- and silicone-

containing dendrimers have appeared in the literature.26–32

3 Polysiloxanes (silicones) and related polymers

The field of polysiloxanes is the most mature area of inorganic polymer science and a

large number of papers were published in 2006. Consequently, there is not enough

space to highlight all the developments in this vast area and this section will focus on

advances in the synthesis of novel silicone macromolecules.

Weber and coworkers have prepared a monomer containing a tricyclic and

tetracyclic siloxane ring (1) and have selectively polymerized the tricyclic ring using

anionic and cationic ROP to prepare 2.33 This interesting development represents the

first selective polymerization of one ring of a bicyclic siloxane monomer and could

prove to be a valuable route to copolymers and crosslinked macromolecules.

Polystyrene-polysiloxane multiblock copolymers 3 with moderate molecular weight

(ca. 25 000 g mol�1) were synthesized from hydrosilylation coupling and were

408 | Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407–427


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characterized by differential scanning calorimetry (DSC) and scanning electron

microscopy (SEM).34 Poly(ethylene oxide)-polydimethylsiloxane-poly(ethylene

oxide) triblock copolymers were observed to form aggregates with a variety of

morphologies that can be controlled by altering the self-assembly conditions.35

Two different strategies have been developed for the preparation of polydi-

phenylsiloxane-polydimethylsiloxane-polydiphenylsiloxane triblock copolymers.36

The anionic ring-opening polymerization (ROP) of hexamethylcyclotrisiloxane

(D3) using the bifunctional initiator Li2(Ph2SiO2) followed by treatment with

hexaphenyltrisiloxane affords polymer 4. In the second strategy, the hydrosilylation

of vinyl-terminated polydiphenylsiloxane with a,o-bis(hydrido)polydimethylsilox-

ane is employed to afford triblock copolymer 5. The number average molecular

weights (Mn) for these novel copolymers ranged from 8800 g mol�1 to 31 300 g

mol�1 with polydispersity indices (PDIs) ranging from 1.4–1.8.



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Alternating copolymers (8) were obtained from the hydrosilylation of the divinyl

monomer 6 with the Si–H terminated oligosiloxane 7.37 The coupling of oligosilane 7

(2100–4000 g mol�1) with 6 afforded the copolymer 8 with molecular weights up to

78 100 g mol�1.

Poly(dimethylsiloxane) zinc and sodium ionomers (0.3–1.3 mol% of metal) have

been prepared and their gel formation has been described.38 Chojnowski and



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coworkers have completed oligomerization reactions of 9 in the presence of B(C6F5)3to form oligosilicone 10 (m = 1, 2, etc.).39 The formation of 10 was accompanied by

hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and dimethylsi-

lane. Kinetic studies to elucidate the mechanism of chain formation are described.

Siloxane oligomers with ethylene glycol side groups 11 were prepared from either

hydrosilation or dehydrocoupling reactions to test their use as electrolytes for

lithium batteries.40 After doping with lithium bis(oxalato)borate or lithium bis(tri-

fluorosulfonyl) imide, ambient temperature conductivities between 2 � 10�4 S cm�1

and 6 � 10�4 S cm�1 were obtained. Polysiloxanes with pendant glycol and methoxy

silane groups allow for the formation of comb structures which are of interest as

electrolyte membranes.41 Rodlike polysiloxanes with acrylamido side groups have

been prepared and crosslinked to prepare hydrogels.42

Polycondensation of monomer 12 with water (1 equiv.) in the presence of catalytic

quantities of tetrabutylammonium fluoride (or HCl) produced insoluble powders.43

X-ray diffraction data suggested that these solids are ordering themselves on the

nanometer scale. A mesoporous material with free phosphines was synthesized and

proved capable of complexing several lanthanide ions.44

A cis-isotactic ladder polysilsesquioxane (14) was obtained in a confined supra-

molecular channel.45 This exciting development was made possible by employing

dischotic Si-substituents, which self-assemble to form H-bonded channels (i.e. 13)

prior to their base-catalysed condensation to form the ladder structure 14. Poly-

silesquioxane materials with bound sulfonic acid groups have been prepared and



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investigated as proton exchange membranes for fuel cell applications. Moreover,

their conductivity was found to increase as a function of sulfonic acid content up to a

maximum of 6.2 � 10�3 S cm�1.46

Polystyrene-block-butadiene-block-polystyrene was grafted with oligomeric silses-

quioxanes using hydrosilation to afford the functional polymer 15.47 The morpho-

logy of the copolymer was investigated using small angle X-ray scattering (SAXS)

and rheology. Miniemulsion (co)polymerization of styrene and g-methacryloxy-

propyltrimethoxysilane has been used to synthesize organic-inorganic nanocapsules

which have been characterized by transmission electron microscopy (TEM),

dynamic light scattering, NMR and IR.48

4 Polysilanes, polygermanes, polystannanes, polycarbosilanes and

related polymers

It is widely known that performing polymerization reactions in chiral solvents can

influence the tacticity and/or helicity of the resultant polymer. In a surprising

development, Holder and coworkers have shown that the Wurtz polymerization

of silanes in a chiral solvent can also influence the molecular weight of the resultant

polysilane.49 Specifically, the Wurtz-type polymerization of PhMeSiCl2 in enantio-

nerically pure (R) or (S)-limonene produced helical polymer 16 with double the

molecular weight than if the analogous polymerization was performed in racemic (R/

S)-limonene at 90 1C. The authors suggested that a reduction in helical reversals in

chiral solvents is responsible for the higher molecular weights.



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Helical polysilanes with fluoroalkyl substituents (17) have been prepared and

analysis of isolated polymer chains by AFM revealed that the polymer topology was

related to the chain length.50 In particular, the longer chains tend to adopt circular

structures whilst the shorter chains form rods. It was shown that the chiral

supramolecular complexation of the helical amylose to oligosilane Me(SiMe2)6Me

was pH-dependent and that the optical activity switched from an ‘‘on’’ to an ‘‘off’’

state at pH r 7.51 CD spectroscopy was used to study aggregates of the solutions of

optically active polysilane 18 in ethanol (a nonsolvent) and THF (an associative

solvent) which were confined to microcapsules.52

Bromo-functional polysilane 19 was reacted with an azocrown complex to afford

photosensitive polysilane 20 (Mn = 70 000 g mol�1; PDI = 1.2).53 Interestingly, UV

irradiation of solutions of 20 with 400 nm filtered light resulted in 65–70% trans–cis

isomerization as indicated by the enhancement of the band at 480 nm characteristic

of n–p* transition of cis-configured azobenzene. Polymethylphenylsilane-supported

Pd and Pt nanoparticles have been used as solid recoverable supports for catalytic

Suzuki, Sonagashira and hydrosilylation reactions.54

Polysilanes with all anti conformations of the main chain (i.e. SiSiSiSi dihedral

angles of 1801) are believed to provide the highest degree of s-conjugation. A major

step towards the realization of an all-anti-polysilane was made with the synthesis of a

(tetramethylene)-tethered octasilane 21 by Fukazawa, Tsuji and Tamao. Currently,

this is the longest silicon chain where the silicon atoms are conformationally

controlled to be in the all anti state. Remarkably, octasilane 21 exhibits a molar

extinction coefficient 3� larger than the unrestricted n-Si8Me18 at 0 1C which is

consistent with increased s delocalization in the former.55



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A polysilane-containing ABA block copolymer 22 has been employed to prepare

shaped calcium carbonate films as 2D model systems for CaCO3 biomaterials

through a photolithographic process.56 In particular, a thin film of amorphous

CaCO3 was deposited onto 22, which had previously been UV-irradiated through a

mask. Subsequent washing of the film with EtOH resulted in the selective removal

of the CaCO3 from the irradiated lanes leaving patterned CaCO3 films (ca. 200 mm�30 nm). Thin films of poly(di-n-hexylsilane) absorbed on a poly(vinyl alcohol)

substrate have been examined to determine the effect of film thickness on molecular

orientation.57 Polycarbosilane was grafted with poly(methyl methacrylate) (PMMA)

or polystyrene (PS) to form random copolymers 23.58 Molecular weights of the

PMMA copolmers ranged from 17 000–19 000 g mol�1 (PDI = 2.1–5.0) whereas the

styrene copolymers exhibited molecular weights from 13 000–20 000 g mol�1 (PDI

= 2.2–2.6).

Cationic, water soluble, conjugated polysilanes were prepared which exhibited

blue-emission and were highly sensitive to quenching agents such as [Fe(CN)6]4–

making them attractive as sensors.59 Low molecular weight poly(dimethylsilane) and

poly(dimethylstannane) were prepared from the electropolymerization of Me2SiCl2and Me2SnCl2, respectively.

60 Ladder polysilanes with 8–18 Si atoms were synthe-

sized which exhibit a double helix structure in the solid state.61 Poly(hydrosilane)s of

the type [RSiH]n have been prepared using metal-catalyzed dehydrocoupling and

their hydrosilation chemistry was explored.62 The synthesis and properties of silylene

phenylene polymers bearing optically active side groups has been studied.63



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Mixed copolymers of organosilane–organogermane and organosilane–organo-

stannane were prepared using the Wurtz coupling reaction of group 14 dichloro

precursors.64 EXAFS and XANES studies on the poly(silane-co-stannane) were

employed to elucidate bond lengths in the polymer [Sn–Sn = 2.82 A, Sn–Si =

2.58 A, Sn–C = 2.15 A]. Oligogermanes have been prepared using sequential

reaction chemistry to add each new germanium atom.65 This study provides a new

route to oligogermanes via hydrogermolysis and may facilitate the tailoring of

oligomer properties through substituent tuning. ADMET polymerization was

employed to form macromolecules containing germanium with molecular weights

(Mw) between 7400 and 19 100 g mol�1.66

5 Polyphosphazenes, polyheterophosphazenes and related polymers

The isolation of the first PH-functionalized polyphosphazene by Niecke and co-

workers represents a remarkable achievement in inorganic polymer science.67 The

polymer 24 was prepared by the ammonolysis of bis(dimethylamino)choropho-

sphine at low temperatures. Interestingly, analysis of the high polymer by NMR

spectroscopy showed signals assigned to Me2N(HNQ)P(H)– and –NQP(H)-

(NMe2)2 end groups in a polymer with about 500 repeating units. Further char-

acterization of PH-polymer 24 by static and dynamic light scattering determined the

weight average molecular weight (Mw = 41 000 g mol�1) and hydrodynamic radius

(Rh = 4.7 nm). Insight into the mechanism of polymerization was obtained from ab

initio calculations.

Manners and coworkers have communicated the first P-donor-stabilized phos-

phoranimine cation [nBu3P–PMe2QNSiMe3]Br.68 Surprisingly, attempts to replace

the electron donating nBu3P moiety with electron withdrawing phosphites [i.e.

(RO)3P; R = Me, Et or Ph] resulted in the quantitative formation of high molecular

weight polyphosphazene. Both polymethylphenylphosphazene [NQP(Me)Ph]n and

polydimethylphosphazene [NQPMe2]n were synthesized with molecular weights

above 100 000 g mol�1).

The self-assembly of oligopeptide grafted cyclotriphosphazenes in aqueous solu-

tion has been reported.69 These novel micelles are of interest for applications in drug

delivery, surfactants and surface modifiers. The use of polyphosphazenes for the



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controlled release of drugs such as human growth hormone, dextran, albumin,

doxorubicin, indomethacin and 5-fluoroacil continues to attract attention.70–74

Polymer 25, an amphiphilic triblock copolymer, was prepared using the cationic

polymerization of phosphoranimines.75 The number average molecular weight (Mn)

for the copolymers ranged from 26 000–55 000 g mol�1. In water, the polymers

formed novel spherical micelles, which were imaged using TEM. Amphiphilic

polyphosphazenes with poly(N-isopropylacrylamide) substituents have been studied

for their self assembly properties to form nanospheres.76,77 Several studies on the

degradation of amino ester functionalized polyphosphazenes were reported and their

possible biomedical applications were considered.78–80 Andrianov and Chen pre-

pared polyphosphazene microspheres which are of interest for microencapsulation

of proteins and are possible vaccine delivery agents.81

Macromolecular substitution of [NQPCl2]n provides a versatile route to polypho-

sphazenes with diverse properties. Polyphosphazenes bearing pyridyl-functionalized

substituents were employed as macromolecular ligands for transition metals to form

organometallic polymers 26 [MLn =W(CO)5, Mn(MeC5H4)(CO)2, FeCp(dppe) and

RuCp(PPh3)2].82 Pyrolysis of these phosphazenes afforded metal nanostructures,

which were found to be metal/metal oxide nanocomposites (for tungsten) and metal

phosphates (for manganese). In a related study, TEM images provided strong

evidence for nanocluster formation in the pyrolysis of mixed-polymer 27.83 Polyphos-

phazenes bearing W(CO)5 moieties in the side group structure exhibit complete

decarbonylation below 300 1C to afford a metallic species which has a stabilizing

effect on the polymer matrix.84 Interestingly, the pyrolysis of polyspirophosphazenes

bearing AuCl moieties in the side group structure affords gold nanostructures of

varying size (up to 130 nm).85 The pyrolysis of a carborane-substituted polypho-

sphazene affords microsize and nanosize BPO4 as suggested by SEM-EDAX, TEM

and X-ray analysis.86

Polymer electrolytes based on poly(phosphazenes) have been the subject of several

studies in the past year. The functionalization of poly[bis(methoxyethoxyethoxy)-

phosphazene] (MEEP) with silicon alkoxide and subsequent hydrolysis using sol–gel

techniques afforded polyphosphazene-silicate hybrid networks.87 The lithium-ion

conductivities of polynorbornenes bearing cyclotriphosphazene side-groups and

polyphosphazenes with bis(2-methoxyethyl)amino side substituents have been in-

vestigated.88,89 The ionic conductivities of polyphosphazenes with sulfonimide and



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oligo(oxyethylene) side groups were investigated.90,91 Redox responsive phospha-

zenes with carboxylic acid side groups have been studied.92

Several norbornene monomers functionalized with cyclotriphosphazene have been

polymerized using ROMP.93 Optically active polyphosphazenes have been prepared,

characterized and studied using fluorescence spectroscopy.94,95 Coumarin and oxime

containing polyphosphazenes have also been synthesized.96,97 Hydroxyapatite-poly-

phosphazene polymer composites have been prepared in vivo as possible bone

analogs.98

6 Other main group element-containing polymers

The synthesis of p-conjugated materials incorporating main group elements in the

main chain continues to attract attention for their possible electronic applications.

Poly(p-phenylenephosphaalkenes) (PPP’s i.e., 28) are formally analogues of poly-

(p-phenylenevinylene) (PPV) where PQC bonds rather than CQC bonds space

phenylene moieties.99 A series of model compounds and polymers were prepared and

it was determined that modifying steric constraints provided a degree of stereo-

chemical control. In particular, employing bulky P-aryl substituents preferentially

affords the Z-phosphaalkene isomer with trans phenylene moieties. The Z-PPP 28

displays a dramatic red shift (Dl = 70 nm) in the UV-Vis spectrum as compared to

the Z model compound 29.

There is continued interest in the preparation of p-conjugated phosphole-

containing materials. Specifically, diarylphospholes have been incorporated into

electroluminescent devices and studied using Raman spectroscopy.100,101 Reau

and coworkers prepared AuCl-protected monomer 30 and electropolymerization

afforded the phosphole-modified poly(thiophene) 31.102 The three-coordinate

phosphine polymer 32 can be prepared from insoluble 31 by immersion of

a thin film of 31 into a 0.1 M solution of PPh3. Polymer 32 was shown to be

useful as an elemental chalcogen detector. Several phosphole derivatives were shown

to exhibit slight antiaromatic character upon oxidation of the P centre with S8.103



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Dithieno[3,2-b:2030-d]phospholes of the type 33 have been the subject of several

studies in 2006.104–106 Of particular significance to the area of inorganic polymer

science was the successful coupling of dibromo phosphole 33 and the bis(boronic

acid) to afford polymer 34 (Mw = 9800; PDI = 1.7).104 The absorbance maxima of

thin films of polyphosphole 34 are red shifted in comparison to that for solutions of

34 which suggests intermolecular p-stacking in the solid. Dithieno[3,2-b:20,30-d]

phospholes bearing Me2Si–H end-groups undergo dehydrocoupling in the presence

of a platinum catalyst to afford polymer 35.106 Interestingly, the Si–H functionality

can also be exploited for hydrosilation with bisalkynes to form dithienophosphole

silyl vinylene polymers.

The first ambient temperature living anionic polymerization of phosphaalkenes

was established.107 Monomer 36 was reacted with substoichiometric amounts ofnBuLi to afford macromolecules 37 with controlled chain lengths. Studies of the rate

of the anionic polymerization of 37 using 31P NMR spectroscopy allowed for the

determination of the rate constant for propagation (kp = 21 L mol�1 h�1).

Remarkably, this rate of propagation is several orders of magnitude lower than

that of styrene. Interestingly, the initiation of 36 with living polystyrene afforded

polystyrene-block-poly(methylenephosphine) 38.

The anionic ROP of a strained phosphirene 39 (monomer:nBuLi = 51:1) has

produced the first polyvinylenephosphines 40 with the sulfurized derivatives showing

modest molecular weights (Mw = 18 000 g mol�1; PDI = 1.23).108 Novel helical

phosphorus-containing polymers with chiral P atoms in the side group structure

were prepared and characterized.109



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Cyclooligostibine (41) has been copolymerized with phenylacetylene to afford

poly(vinylene stibine) (42) with Mw’s up to 8100 g mol�1.110a These remarkable

polymers have been prepared in an analogous fashion to the formation of their

arsenic analogues. The first synthesis of a bismole-containing polymer 43 has also

been reported.110b

Boron-containing macromolecules have been the subject of recent studies and

are attractive synthetic targets. Mixing the difunctional fc(BBr2)2 (where fc =

(Z5-C5H4)2Fe) with HSiEt3 produced the borylene-bridged poly(ferrocenylene)s

44a.111 These novel macromolecules possess a vacant p orbital on the B atom,

which interacts with the p-structure of the fc moiety to promote electron delocaliza-

tion in the polymer. Although polymer 44a is air- and moisture-sensitive, replace-

ment of the B–Br moiety by treatment with [CuMes]n affords the moderately air



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stable polymer 44b (Mn = 5160 g mol�1; PDI = 1.45). Jakle and coworkers have

also prepared a boron modified polystyrene from the reaction of poly(4-trimethylsi-

lylstyrene) and BBr3.112 Interestingly, introduction of mixed B-thiophene/B-mesityl

substituents through nucleophilic substitution at the B–Br centre resulted in strongly

emissive polymers in the blue, yellow or yellow-green regions.

A highly crystalline framework based on poly(boronate ester) linkages has been

successfully prepared and characterized.113 Ionic liquids bearing organoboron units

have been synthesized for lithium ion transport.114 Poly(organodecaboranes) have

been prepared and have been investigated as boron–carbide precursors.115 The

synthesis and polymerization of the carborane CH2QCH(CH2)n–2C(BMe)11�Li+

(n= 6) has been described and a detailed study on the mechanism of polymerization

is outlined.116 Boron-containing poly(vinyl alcohol) has been prepared via conden-

sation methods and studied for use as a ceramic precursor.117 A borazine derivative

was reported as a single source precursor for Si/B/N/C ceramics.118

Catenation is a common phenomenon for the Group 14 elements however Group

13 elements rarely display the same behaviour. In a remarkable advance, Hill and

coworkers have prepared a catenated indium chain 45 from treatment of indium(I)

iodide with protonated N-xylyl b-diketiminate and KN(SiMe3)2.119 Each of the 4

internal indium centres are complexed by one b-diketiminate ligand with bonds to

two of the flanking indium atoms. The formal oxidation state of the internal indium

atoms is +1. The outer indium atoms are bonded to one b-diketiminate and one

iodide ligand as well. This remarkable structure will provide new avenues to explore

the preparation of catenated indium polymers.

7 Ferrocene-containing and related organometallic polymers

A series of strained [1]silatrochrocenophanes (i.e. 46) were prepared and structural

characterization revealed moderate ring tilt angles (ca. 151). Treatment of 46 with an

equimolar amount of a platinum catalyst [i.e. Pt(PEt3)4] resulted in oxidative

addition and insertion of Pt into the Si–C(Cp) bond; the first step in ring-opening

polymerization. Importantly, using catalytic quantities of platinum catalyst resulted

in polymerization to afford novel metallopolymers (47) with modest molecular

weights (Mw = 6.4 � 103 g mol�1 with PDI = 1.6).120

The investigation of ferrocenylsilane block copolymers continues to attract

considerable attention due to the exciting properties of these metal-containing

systems. The photocontrolled living polymerization of ferrocenophanes has been



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used to prepare block copolymers with controlled architectures.121 Photoirradiation

at wavelengths above 310 nm weakens the Fe–Cp bond of the ferrocenophane 48

making it susceptible to attack by weak, functional group tolerant, initiators. Once

the monomer has been completely consumed, the living polymer 49 can be quenched

to form 50 (Mn = 17 900 g mol�1 PDI = 1.09) or it could be used to initiate other

anionic polymerizations and synthesize block copolymers.

Several papers have appeared in the past year which describe the self-assembly

properties of polyferrocenylsilane block copolymers,122–124 the application of self-

assembled copolymer films as catalysts for carbon nanotubes with tunable dia-

meters,125 and the use of ferrocene copolymers as templates for nanotextured

surfaces.126 An electron-rich ferrocenylsilane polymer bearing tert-butyl substituted

cyclopentadienyl moieties has been studied via cyclic voltammetry and its redox

behaviour suggested significant Fe� � �Fe interactions.127 Polyferrocenylsilanes have

been studied as model systems for redox-driven macromolecular motors.128,129 The

functionalization of poly(ferrocenylchloromethylsilane) with alkoxy benzyl ether

monodendrons affords novel cocoon-like nanostructures with iron-rich cores and

dimensions of ca. 16 nm � ca. 2.4 nm (from AFM) and hydrodynamic radii of ca.

7 nm (from dynamic light-scattering).130

Manners and coworkers have employed polyferrocenylsilanes functionalized with

cobalt cluster pendant groups as precursors to magnetic CoFe alloy nanoparti-

cles.131 Remarkably, when the polymer films are pyrolyzed at 600 1C the nanopar-

ticle-containing ceramic films are superparamagnetic whilst at higher pyrolysis

temperatures the films are ferromagnetic. Polyferrocenylsilanes have also been used

to quench platinum octaethylporphine phosphorescence.132 Interesting [2]ferroce-

nophanes containing C–Pb and C–Zr bridges have been prepared and fully

characterized, however attempts to induce polymerization using both thermolytic

and metal-catalyzed methods were unsuccessful.133

Chiral ferrocene-based vinyl monomers have been grafted onto commercially

available polymethylhydrosiloxane and optically active liquid crystals were ob-

tained.134 Conducting polythiophenes containing azaferrocene moieties in the main

chain (i.e. 51) have been synthesized and their in situ conductivities (s = 0.0047–

0.0095 S cm�1) and their spectroelectrochemical properties were investigated.135

Oxidative coupling polymerization was used to prepare an electroactive polyamide

containing ferrocene with high molecular weight (Mw = 9.97 � 104 g mol�1; PDI =

1.77). The conductivity of the doped polymer was found to be 7.6 � 10�7 S cm�1.136



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ROMP of norbornene continues to attract attention for the preparation of

interesting polymers (52) with organometallic moieties as pendant functionalities.137

Aziz and coworkers have prepared organoiron polymers with azo dye moieties and

investigated their photostability.138,139

Iron-containing dendrimers continue to be the subject of numerous studies.

Astruc and coworkers prepared 9-, 16- and 27-branched dendrimers with

[{CpFe(m3-CO)}4] clusters at the periphery.140 These systems were investigated for

their interesting redox properties and found to be useful sensors for oxo anions. A

series of ferrocenylazobenzene dendrimers were prepared and irradiation with UV

light led to trans–cis isomerization.141 The preparation of remarkable molecular

wheels incorporating 10 Fe centres stack in a p fashion to prepare tubular structures

in the solid state.142

8 Polymers containing skeletal d-block elements

Anderson and co-workers have reported that butadiyne linked porphyrin oligomers

53 (up to 8 monomer units) self assemble into a coplanar structure by the addition of

bipyridine forming 54.143 These oligomeric ladder complexes (where n 4 2) show a

significant red shift in their two-photon absorption with respect to 53. This apparent

increase in conjugation length is attributed to the increase in coplanarity of the

double strand porphyrin ladders due to interaction of the bipyridine ligand with the

Zn metal atoms. In a related study by Chujo and coworkers, conjugated zinc

porphyrin dimers have been shown to form molecular tubes.144 An azopyridine-

functionalized acrylate polymer (Mn = 12 600 g mol�1; PDI = 1.8) was complexed

to Zn and Co porphyrins and studied for changes in redox behaviour.145

Interesting rigid-rod polymers (55) containing alternating {Pt6} clusters and

conjugated alkynyl moieties have been synthesized with molecular weights up to

148 000 g mol.146 The UV-Vis absorption spectra of these complexes suggests that

some electron delocalization along the backbone has been achieved. Pd–pincer

complexes were also employed as a route to supramolecular cruciforms.147 By

controlling the feed ratio of the two starting materials, polymer 56 could be formed

in solution and was characterized using viscosity measurements.



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Thiophene monomers containing Co sandwich structures have been polymerized

and studied as sensors for nitric oxide.148,149 Polymers with b-diketonate units

coordinated to Ir in the main chain have been prepared by Suzuki cross coupling.

Moderate molecular weights of this metal-containing polymer were achieved using

this methodology (Mn = 10, 200 g mol�1; PDI = 1.4).150

In an attempt to prepare metal coordination polymers from an Au diphosphine

complex and bispyridine, evidence for oligomers with up to 16 gold atoms were

observed in solution (CH2Cl2) by electrospray mass spectrometry (2463 amu).151 In

combination with NMR and ESI-MS, the authors speculate there is a complex

equilibrium between cyclic species and linear polymers. This remarkable ring open-

ing polymerization of labile coordination bonds represents a new route to Au

containing polymers.

Abbreviations

ADMET acyclic diene metathesis

ROP ring-opening polymerization

DSC differential scanning calorimetry



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SEM scanning electron microscopy

TEM transmission electron microscopy

SAXS small angle X-ray scattering

NMR nuclear magnetic resonance

AFM atomic force microscopy

ROMP ring-opening metathesis polymerization

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130 K. T. Kim, J. W. Han, C. Y. Ryu, F. C. Sun, S. S. Sheiko, M. A. Winnik and I. Manners,Macromolecules, 2006, 39, 7922.

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inorganic and organometallic polymers

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