Inorganic and organometallic polymers

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  • 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 PH 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, 407427 | 407

    This journal is c The Royal Society of Chemistry 2007

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  • 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 siliconcarbon 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 FC interactions of fluorosilane polymers have been highlighted.9Several 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 byBaumgartner 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.2632

    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 mol1) were synthesized from hydrosilylation coupling and were

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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 mol1 to 31 300 g

    mol1 with polydispersity indices (PDIs) ranging from 1.41.8.

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

    monomer 6 with the SiH terminated oligosiloxane 7.37 The coupling of oligosilane 7

    (21004000 g mol1) with 6 afforded the copolymer 8 with molecular weights up to

    78 100 g mol1.

    Poly(dimethylsiloxane) zinc and sodium ionomers (0.31.3 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 2 104 S cm1and 6 104 S cm1 were obtained. Polysiloxanes with pendant glycol and methoxysilane 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 6.2 103 S cm1.46

    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 andrelated 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 inchiral 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 ofoptically 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 mol1; PDI = 1.2).53 Interestingly, UV

    irradiation of solutions of 20 with 400 nm filtered light resulted in 6570% transcis

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

    of np* transition of cis-configured azobenzene. Polymethylphenylsilane-supportedPd 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 majorstep 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 isconsistent 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 mm30 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 00019 000 g mol1 (PDI = 2.15.0) whereas the

    styrene copolymers exhibited molecular weights from 13 00020 000 g mol1 (PDI

    = 2.22.6).

    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 818 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 organosilaneorganogermane and organosilaneorgano-

    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 [SnSn = 2.82 A, SnSi =

    2.58 A, SnC = 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 mol1.66

    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 mol1) 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 [nBu3PPMe2QNSiMe3]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 andpolydimethylphosphazene [NQPMe2]n were synthesized with molecular weightsabove 100 000 g mol1).

    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.7074

    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 00055 000 g mol1. 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.7880 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 stabilizingeffect 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 solgel

    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

    416 | Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407427

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

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

    (p-phenylenevinylene) (PPV) where PQC bonds rather than CQC bonds spacephenylene 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 tothe 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 2006.104106 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 Me2SiH end-groups undergo dehydrocoupling in the presence

    of a platinum catalyst to afford polymer 35.106 Interestingly, the SiH 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 mol1 h1).

    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 mol1; 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 Mws up to 8100 g mol1.110a 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)s44a.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 BBr moiety by treatment with [CuMes]n affords the moderately air

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  • stable polymer 44b (Mn = 5160 g mol1; 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 BBr 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 boroncarbide precursors.115 The

    synthesis and polymerization of the carborane CH2QCH(CH2)n2C(BMe)11Li+

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

    addition and insertion of Pt into the SiC(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 mol1 with PDI = 1.6).120The 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 FeCp 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 mol1 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,122124 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 havebeen 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 CPb and CZr 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 = 0.00470.0095 S cm1) 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 mol1; PDI =1.77). The conductivity of the doped polymer was found to be 7.6 107 S cm1.136

    Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407427 | 421

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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 transcis isomerization.141 The preparation of remarkable molecular

    wheels incorporating 10 Fe centres stack in a p fashion to prepare tubular structuresin 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 asignificant 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 mol1; 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. Pdpincer

    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.

    422 | Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407427

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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 unitscoordinated 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 mol1; 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

    Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407427 | 423

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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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    Annu. Rep. Prog. Chem., Sect. A, 2007, 103, 407427 | 427

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