inorganic and organometallic polymers

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

This journal is © The Royal Society of Chemistry 2013

Cite this: DOI: 10.1039/c3ic90026f

Inorganic and organometallic polymers

Fumitoshi Katoa and David A. Rider*ab

DOI: 10.1039/c3ic90026f

This article provides an inexhaustive overview of research selected from the 2012 scientific

literature involving polymers with inorganic elements as a key part of their structure.

1. Highlights

The strategy for incorporating inorganic elements into polymers and macro-molecular systems has often led to new properties and capabilities that wouldotherwise be challenging for purely-organic analogues to achieve. The increasingresearch activity in inorganic and organometallic polymers is a testament to theopportunity for advancing our fundamental understanding of polymer scienceand for triggering innovation in various technologies. In 2012 highlights in thetopic of inorganic and organometallic polymers include: the fabrication of bulkheterojunction (BHJ) solar cell featuring a benzodiselenophene copolymer whichoperated with a power conversion efficiency (PCE) of 6.87%,90 the synthesis of lowband-gap poly(naphthalene-diimide-alt-biselenophene),94 the electropolymerisationof poly(3-alkyltellurophene)s,93 the preparation of silole-containing poly(silylene-vinylene)s,68 quaternised poly(aryloxy- and alkoxyphosphazenes)24 and fluorinatedpoly(arylene ether phosphine oxide) with pendant iridium complexes,33 the prepara-tion and self-assembly of peptidic-polyferrocenylsilanes,103 and the step-growthpolymerisation porphyrin dialynes and diiodoaryl monomers to afford doubly-strapped porphyrin linked groups in the main polymer chain.118

This review article adopts a similar organisational format to the previous 2011Annual Report in this series. An overview of the recent books and review articles in thedomain of inorganic and organometallic polymers will be given followed by sectionsdiscussing boron-containing polymers. Sections highlighting polyphosphazenes andother phosphorus-based polymers will then be covered followed by sections outliningnew findings in other polymers containing main-group elements (sulfur-containing,silicon-containing etc.). Thereafter, Se- and Te-containing polymers will be reviewedfollowed by sections covering developments in metallocene polymers. Lastly, sectionson rare earth-containing and metal-porphyrin-based polymers are included.

a Department of Chemistry, Western Washington University, 516 High St., Bellingham, WA 98225 USAb Department of Engineering Technology, Western Washington University, 516 High St., Bellingham,

WA 98225 USA

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http://dx.doi.org/10.1039/c3ic90026f

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Throughout this article, primary attention will be given to discussing thesynthesis (with a briefing on the characterisation used by the authors) and novelproperties of new, covalently linked, macromolecules wherein inorganic elementsrepresent an integral component of their core structure.

2. Books and reviews of inorganic and organometallicpolymers

In 2012, several publications have summarised various aspects of inorganic andorganometallic polymer science. A brief summary of these publications is listedin this section.

Recent progress in the synthesis of polysilanes and an overview about certainapplications was presented in the book ‘‘Silicon Polymers – Advances in PolymerScience.’’1 The journal Macromolecular Chemical and Physics presented a specialseries issue devoted to ‘‘New Frontiers in Functional Polymers’’ which included areview article on ‘‘Metal-Free and Metallated Polymers: Properties and Photo-voltaic Performance.’’2,3

Similarly, as the field of polymer solar cells (PSCs) continued to grow,contributions from organic–inorganic conjugated polymers have been especiallywelcomed. Progress in the design of PSCs with high power conversion efficiency(PCE) have been reviewed by You and also proposed theoretical rules to rationallydesign and predict the performance of PSCs.4 Review articles discussing currentadvancements in solar cells composed of organic–inorganic polymers and metal-oxide nanocrystals have also been published.5,6 Katz et al. recently highlightedthiophene, selenophene, benzobisthiadiazole, and benzobisthienosilole typesemiconducting polymers for n- and p-type field effect transistors.7

Applications of polymers containing transition-metal complexes (PTMCs) foroptoelectronic devices have also been demonstrated in an increasing amount.A review by Huang and co-workers summarised the current trends, advantagesand disadvantages of PTMCs for optoelectronic devices.8 Strohm and Abd-El-Azizreviewed the field of transition metal-containing macromolecules – particularly intheir synthetic methodologies, structural properties and applications.9 Recentdevelopments in the synthesis and application of metal-functionalised polymersvia electropolymerisation were reviewed by Schubert et al.10

Nishihara published a book dedicated to the current advancement in inorganicpolymer synthesis via metal-catalysed cross-coupling reactions.11 A review on theprogress towards the synthesis and photostability of polystannanes was reported.12

Highlights of the recent progress in morphologies, structures, compositions, andapplications of transition metal modified polymer derived ceramics (PDCs) werereported.13

3. Boron-containing polymers

RAFT polymerisation was used by the group of Sumerlin to prepare the boronicacid functionalised block copolymer: poly(N,N-dimethylacrylamide)-block-poly-[N-(2-acryloylamino-ethyl)-4-boronobenzamide]. The sensitivity of the pendantphenylboronic acid moieties to pH and to glucose concentration was used as atrigger for solution assembly–disassembly.14 Chiral polymers consisting of styryl

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boron dipyrromethenes and 1,10-binaphthyl units were synthesised via Sonogashirapolymerisation. The organoboron polymers (Mn = 7780–10 890; PDI = 1.8–2.0)exhibited excellent anisotropic NIR fluorescence with a maximum in the fluores-cence spectra at 658–714 nm.15

Nitroxide-mediated copolymerization of 4-methylstyrene and 4-acetoxystyrene(in a 2 : 1 and 4 : 1 ratio) afforded a copolymer capable of functionalisation with aboron subphthalocyanine. Deacetylation of the acetoxy groups on the copolymerand subsequent reaction with bromo boron subphthalocyanine yielded the poly-(4-methylstyrene)-co-poly(phenoxy boron subphthalocyanine) (1) in B60% (PDI =5.65–8.34; Mw = 8.7 � 103 to 1.76 � 104 g mol�1). The boron subphthalocyaninylpolymers exhibited strong absorption at 564 nm and relatively low quantumyields.16 The Jakle group synthesised novel benzodiazaborolyl-functionalised poly-styrenes (2) that exhibited high quantum yield of 77% and therefore offer potentialefficient host materials for transition metal-based triplet emitters for polymer light-emitting diodes (PLEDs).17 Jakle’s group has also prepared a series of luminescentorganoborane quinolato block copolymers. Block copolymers with polystyrene (PS),PS-co-polymaleic anhydride P(St-alt-MAh), and poly(N-isopropylacrylamide)(PNIPAM) segments linked to organoborane quinolato blocks were created from areversible addition-fragmentation termination (RAFT) polymerisation strategy.18

Wang and co-workers used Grignard metathesis route for the preparation of a novelheat resistant boron-containing poly(silyleneethynylene) termed a hybrid polymer ofboron–silicon and acetylene (PBSA) (3). Thermogravimetric analysis (TGA) and differ-ential scanning calorimetry (DSC) analysis of the polymer confirmed its ability to act asan effective matrix material for high-temperature composites.19 The reaction betweentris(dichloromethylsilylethyl)borane and methylamine yielded oligomeric boron-modified polysilazanes ([B(C2H4SiCH3NCH3)3]n, n = B2.5) (4). The materials werefound to exhibit a ceramic yield of 44% after thermal decomposition at 1000 1C.20

Novel metal- and boron-containing conducting polymers (5) have been synthesisedfrom electropolymerisation of tris(diphenylglyoximato)-bis(bithienylboron)cobalt(II)/iron(II) monomers. The monomers were prepared by a metal-templated condensationreactions between diphenylglyoxime and bithiopheneboronic acid. The presence ofmetal in polymer was confirmed by energy-dispersive X-ray (EDX) analysis and cyclicvoltammetry (CV) was used to verify the retention of metal during polymerisation.Currently, the iron- and cobalt-containing organoboron polymers are being explored

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for electrocatalytic applications.21 The borane termini of a,o-(dibromoboryl)-functionalised telechelic polystyrene were converted to tris(1-pyrazolyl)borate (Tp)moieties and subsequently used for complexation with FeCl2 to afford iron-containingorganoboron polymers (6). The UV-Vis spectrum confirmed the presence of thebridging Tp2Fe(II) units by way of metal-to-ligand charge transfer bands and 1A1g to1T1g charge transfer at 343 and 530 nm, respectively.22

4. Polyphosphazenes (PPNs) and phosphorous-containingpolymers

The photo- and magnetochemical properties of two new PPNs based on ironbis(2,20 : 6020 0-terpyridine)-loaded terpyridinyl-PPNs have recently been studied.Electronic absorbance, proton nuclear magnetic resonance (1H-NMR), 31P-NMR,solid-state resonance Raman, magnetic susceptibility and Mossbauer spectro-scopy were used to characterise the Fe(II)-loaded PPNs. DFT results were used toexplain the possible suppression of interaction between Fe(II) centres with thePPN backbone in the phenyl-extended analogue.23

Allcock and Mallouk et al. recently reported the synthesis of backbone quaternisedpoly(aryloxy- and alkoxyphosphazenes) (7). The degree of methylation of the back-bone nitrogen by methyltriflate was determined by NMR and found to depend on thenature of the shielding effect of substituents at the phosphorus centre. Accordingly,the poly(phenyloxyphosphazene) could be quaternised up to 50 mol% whereas PPNssubstituted with n-butoxy and 2-(2-methoxyethoxy)ethoxy sidechains were onlyquaternised to 21 and 19 mol%, respectively. The quaternised poly(aryloxy- andalkoxyphosphazenes) exhibited ionic conductivities of 2.58� 10�4 S cm�1 and 2.09�10�3 S cm�1 at 25 1C and 80 1C respectively. TGA analysis showed that quaternisedPPNs were less thermally stable than unquaternised counterparts.24 A series ofbioerodible PPNs (8) that contain phosphoester and phosphonic acid substituentswere synthesised via prior or post-side-group attachment. Currently their bioactivityduring exposure to simulated body fluid is being investigated.25 A series of newferrocene containing PN terpolymers (9) were prepared from the PPN copolymerpoly(methylphenylphosphazene)-co-poly(dimethylphosphazene) [(Ph)(Me)PN]x[Me2PN]y.The synthetic methodology involved BuLi deprotonation of methyl sidechainsfollowed by a substitution reaction at ferrocene carboxaldehyde. The redox proper-ties of these polymers were studied by CV and revealed that the redox couple of thependant ferrocenyl groups were shifted towards more positive potential relative tofree ferrocene as a result of the electron-withdrawing nature of the PPN backbone.Moreover the diffusion coefficient of the terpolymers was determined to be mainlyindependent of the degree of substitution with ferrocene groups.26

Other recent developments in PPNs include the understanding of an interestingreversible substituent exchange reaction for poly(alkyloxyphosphazenes). The studyshows that the order of addition of different nucleophiles is crucial for determining


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the composition of co-substituted polyphosphazenes. Trichloroethoxy sidechain groupsfor example were shown to be labile to trifluoroethoxy nucleophiles.27 Accordingly,novel organophosphazenes with trichloroethoxy as the substituent or as cosubstituentof trifluoroethoxy, phenoxy, or methoxyethoxyethoxy groups were also studied. A similarstudy was conducted with short-chain linear oligomeric PPNs.28 Amphiphilic PPNs withdiisopropylamino (DPA) substituents were synthesised and its cell membranepermeability in a certain pH range was recently evaluated. PPNs with a high DPAcontent inhibited P-glycoprotein activity in cells and are currently being investigated forapplications for the treatment of drug-resistant tumors.29 Similarly, novel amphiphilicpoly[bis(trifluoroethoxy)phosphazene]-block-poly[(dimethylamino)ethyl methacrylate]diblock copolymers were synthesised by click functionalising the terminus of the aPPN homopolymer with a 2-bromo-2-methylpropanoate group. Subsequently, atomtransfer radical polymerisation (ATRP) of 2-(dimethylamino)ethyl methacrylate usingthis terminus was completed and, after a dialysis isolation step, afforded the blockcopolymers in sufficient yield for structural studies. The block copolymersundergo self-assembly in water and with a critical micelle concentration in therange of 3.47–9.55 mg L�1 and an average micelle diameter of 100–142 nm.30

Analogously, ATRP was used to graft styrene, tert-butylacrylate or N-isopropyl-acrylamide on sidechain functionalised PPNs.31

A new method for the oxidation of poly(alkylene H-phosphate) by trichloroisocyanuricacid is reported and subsequently used to synthesise poly(methyloxyethylenephosphate) and poly(hydroxyoxyethylene phosphate) (10). The solubility andhydrolytic stability of these polymers are dependent on the controllable ratiobetween H-phosphonate and phosphate units and therefore carry the potential ofbecoming efficient drug carriers.32 Novel fluorinated poly(arylene ether phos-phine oxide) backbone with iridium dyes (11) incorporated is reported withdemonstrated maximum luminous efficiency of 19.4 cd A�1.33

Novel polymer–protein conjugates of pentafluorophenyl (PFP) – ester function-alised phosphorylcholine (PC) conjugated to lysozyme were synthesised. The sizeof the conjugates in solution varied depending on their molecular weights andshape. The activity of the conjugates decreased as the polymer molecular weightincreased possibly due to the steric interference, but in return the pharmokineticsanalysis demonstrated the polymer–protein conjugate to have an extendedelimination half-life of 30 times that of the lysozyme.34

5. Sulfur-containing polymers

Sulfur-containing polymers such as carbazole and diazabenzothiophene have con-tinued to advanced many optoelectronic research areas. Novel spirobifluorene-based


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polymers containing thiophene and benzothiadiazole units were synthesised bySuzuki–Miyaura polycondensation and found to exhibit an optical band gap of1.97 eV. When blended with PC71BM, the BHJ solar cell showed a PCE of 4.6%.35

Similarly, a novel donor–acceptor (D–A) copolymer composed of benzothiophenederivative and fluorinated quinoxaline (12) was obtained by Stille cross-couplingpolymerisation. The blend of fluorinated quinoxaline-based polymer and PC71BMwas used to fabricate a BHJ solar cell and recorded a PCE of up to 8.0%.36

Novel copolymers synthesised from fluorine substituted benzodithiophene-dithienobenzothiadiazole (BnDT-DTBT) (13) monomers were found to haveenhanced open-circuit voltage (Voc), short-circuit current density ( Jsc), and fill factor(FF) due to reduced charge recombination and improved p–p stacking. The BHJsolar cell made from the copolymer and PC61BM blend exhibited PCE of up to 7%.37

Block copolymers composed of P3HT and poly(naphthalene bisimide) (PNBI)segments were synthesised by quasi-living Grignard metathesis polymerisation andYamamoto coupling reactions. The 1.38 eV band gap material allowed for thefabrication of a BHJ photovoltaic device with Voc, Jsc, and PCE as high as of, 0.56 V,4.57 mA cm�1, and 1.28%, respectively.38 Likewise, thienopyrroledione (TPD)containing P3HT-based D–A semi-random copolymers were synthesised via theStille copolymerisation reaction. The maximum external quantum efficiencies (EQE)obtained were 68 and 40% at 680 and 800 nm, respectively.39 3,4-Ethylenedioxy-thiophene (EDOT) was functionalised with acrylate via free radical polymerizationand underwent a secondary electropolymerisation reaction to synthesise PEDOT-PAA.40 PEDOT-PAA showed excellent electrochemical and thermal stability as well ashigh optical contrast ratio and electroluminescent device coloration efficiency of50.9% at 620 nm and 211 cm2 C�1, respectively. In another study by Ferraris et al.dialkoxy and dithioalkoxy side chains were attached to benzo[1,2-b:4,5-b0]-dithiophene (BDT) units and polymerised via Still cross-coupling reaction. Blendsof the polymer with PC61BM gave BHJ photovoltaics with a Voc and a PCE of 0.99 Vand 4.0%, respectively.41 Pyrene-containing poly[N-90-heptadecanyl-2,7-carbazole-alt-5,50-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PCDTBT) and poly[4,8-bis-(2-ethylhexyl-2-thenyl)-benzo[1,2-b:4,5-b 0]dithiophene-alt-5,5 0-(4 0,7 0-di-2-thienyl-20,10,30-benzothiadiazole)] (PBDTDTBT) were synthesised via Suzuki or Stillecross-coupling reaction and the copolymer: PC71BM-based devices recordedPCE as high as 3.22 and 5.04%, respectively.42 Novel copolymers based onthienoisoindoledione (TID) and BDT derivatives were reported. The highestoccupied molecular orbital (HOMO) level of the BDT was tuned by chemicalmodifications to the monomers and achieved PCE as high as 4.8%. X-raydiffraction (XRD) showed lack of order domain in the polymer blend thatcontained TID and the computational modelling suggested the cause to be fromthe twisted backbone of TID.43 Related, a series of novel PNDT derivatives weresynthesised via Stille, Suzuki cross-coupling, and oxidative cyclisation reactionbetween NDT and thiophene. The elongation of p-conjugation length by the


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installed thiophene units was verified with UV-Vis spectra and XRD and atomicforce microscopy (AFM) and ultimately demonstrated increased polymercrystallinity.44 Novel copolymers were synthesised via the Stille cross-couplingreaction between NDT and thieno[3,4-c]pyrrole-4,6-dione (TPD). The BHJ solarcell fabricated from the polymer blend composed of the NDT-based copolymersand PC71BM and operated with a Jsc, Voc, and PCE of 11.54 mA cm�2, 0.69 V, and4.0%.45 Novel copolymers based on thienoisoindoledione (TID) and BDT deriva-tives were reported. 3,6-Carbazole unit was incorporated into BT derivativemonomer to synthesise novel D–A copolymers. The PSC device exhibited PCEas high as 5.1% due to the hole mobility enhanced by 2,6-carbazole.46 Suzukicoupling reaction was used to synthesize a series of [1,2,5]thiadiazolo[3,4-g]-quinoxaline (TQ). In this synthesis, Jo et al. has incorporated butoxy in thepolymer and discovered to lower the lowest unoccupied molecular orbital (LUMO)level as low as �3.6 eV.47

A novel p-type donor–acceptor type p-conjugated copolymer with pendantphenylazomethine (PImCDTBT) was synthesised via Suzuki cross-coupling reac-tion (14). Phenylazomethine serves as a metal ligation site and its complexationwith SnCl2 was reported to enhance Voc values.48 Similarly, a novel DTP-basedcopolymer (15) was produced from dithienopyrroloquinoxaline (DTPQX) viaSuzuki or Stille cross-coupling reaction.49

Double intramolecular Friedel–Crafts acrylation was used to synthesise dithieno-[2,3-b:7,6-b]carbazole-based D–A copolymers.50 Partial fluorination of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b0]dithiophene)-2,6-diyl] (PCPDTBT) wasperformed via microwave-assisted Stille polymerisation and exhibited improve-ments in p–p stacking and hole mobility. The BHJ solar cell fabricated fromPCPDTBT and [2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b0]dithiophene)-alt-4,7-(5-fluoro-[2,1,3]-benzothiadiazole)] (PCPDTFBT) exhibited PCE of 2.73 and6.16% respectively.51,52 A film of novel naphthobisthiadiazole (NTz)-based D–Apolymer was analysed by 2D grazing incidence XRD and found to possess strongp–p stacking structure with a distance of 3.5 Å. The centrosymmetry of NTz-basedpolymer is assumed to allow favourable orientation of the polymer.53 The synthesisof a series of novel ter-polymers, poly-[2,7-(9,90-dioctylfluorene)-alt-5,50-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PFTBT)-based copolymers containing peryleneunits via the Suzuki coupling polymerisation were reported by Hwang et al. Theperylene units gave the polymers enhanced p–p interaction between the polymerchains and the BHJ device fabricated from the polymer blend demonstrated PCE,Jsc, Voc, and FF as high as 3.16%, 9.61 mA cm�2, 0.81 V, and 41%, respectively.54

Novel copolymers composed of 2,8-bis(alkoxy)dibenzothiophene as the acceptorand 3,4-bis(octyloxy)benzothiadiazole or benzothiadiazole as the donor unit werereported by Bo et al.55 Poly((9,9-dioctylfluorene)2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-20,20 0-diyl) (PF8TBT) was synthesised via the Suzuki


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step-growth polycondensation and subsequently terminated by monobrominatedP3HT to give a novel diblock copolymer PF8TBT-b-P3HT. The excess P3HT wasremoved via purification by preparative gel permeation chromatography (GPC) andobtained polydispersity index (PDI) as low as 1.12.56

Suzuki polycondensation between benzothiadiazole (BT) and phenothiazine(PT) or phenothiazine-S,S-dioxide (PT-SS) were performed to synthesise novel D–Acopolymers of PPTDTBT and PPTDTBT-SS (16), respectively. The CV characterisa-tion revealed the HOMO and LUMO energy levels to be �5.41 and �3.63 eV forPPTDTBT and �5.60 and �3.60 eV for PPTDTBT-SS, respectively.57 A novelpoly(phenylenevinylene) (PPV) derivative, poly[2,5-bis-(20-ethylhexylsulfonyl)-1,4-phenylenevinylene] (SO2EH-PPV, 17) was synthesised via Stille coupling reaction.From the CV and optical studies on the polymer, HOMO and LUMO levels werecalculated to be �6.0 and �3.61 eV, respectively.58

Copolymerisation between poly(benzimidazolone sulfone)s and 4,40-biphenolvia N–C coupling polycondensation reaction was reported by Hay et al. (18).59

Disulfanyltricycle[5.2.1.02,6]decane (TCDSH) and bis(vinylsulfone)tricycle[5.2.1.02,6]-decane were polymerised with divinyl sulfone (DVS) or 2,5-bis(sulfanyl-methyl)-1,4-dithiane (BSMD) to synthesise poly(TCDSH/DVS) (19a) and poly(BSMD/VSTCD)(19b). Poly(TCDSH/DVS) and poly(BSMD/VSTCD) had glass transition tempera-tures of 74 and 113 1C, high refractive indices of 1.6052 and 1.6228, and Abbenumbers of 48.0 and 45.8, respectively.60

Photocrosslinked poly(arylene ether sulfone) (SPAEF) (20) containing chalcone unitsin the polymer backbone was synthesised via an aromatic nucleophilic substitutionreaction with 4,40-dihydroxychalcone (4DHC), 4,40-difluoro-diphenylsulfone-3,30-disulfonate (SDFDPS), and decafluorobiphenyl (DFBP) and subsequentlyirradiated by UV light to initiate photocrosslinking. Methanol diffusion coeffi-cient of photocrosslinked SPAEF was found to be hindered due to its densenetwork but the proton conductivity, oxidative, and hydrolytic stabilities weresignificantly enhanced and surpassed those of Nafions 117.61


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6. Polycarbosilanes

The induction of chirality in poly (m- and p-phenylenedisilanylene)s has beendemonstrated. s–p-conjugated polysilanylenes with oligo(ethylene glycol) sidechains (21a; Mn = 8300–8500; PDI = 1.3–1.5: 21b; Mn = 10 300; PDI = 1.15) weresynthesised by reductive coupling of chlorosilane precursors and characterised byGPC, NMR and circular dichroism.62 As the positioning of the chiral centre in theside chain was extended away from the main chain, the induced Cotton effect onthe polysilane was observed to decrease.

Silicon-containing aliphatic poly(ester)s have recently been synthesised frombis(4-hydroxymethyl)phenyl-methyl-alkylsilane (alkyl = methyl, ethyl) and werefound to be soluble in polar aprotic solvents (22). Fourier transform infrared (FT-IR)spectroscopy and multi-nuclear NMR confirmed the structure while TGA showed highthermal stability (up to 337 1C for 10% weight loss; and 34% residue at 900 1C).63

The curing of a polycarbosilane that is based on bridging hexylene–disila-cyclobutane main chain units was investigated (23).64 Curing thin films at 300 1Cwas found to afford a hydrophobic cross-linked polycarbosilane layer with adielectric constant of 2.5 and a resilency to moisture-assisted cracking.

A series of silicon-containing bithiopheneimide-based (BTI) polymers was recentlyprepared (24). The electron-deficient characteristics of the BTI lowered the HOMOlevel of the copolymer and the N-alkyl side chain tuned the solubility of the polymerwhich then allowed for higher degree of lamellar order and p–p stacking. Con-sequently, the copolymer: PC71BM blend-based BHJ solar cells exhibited a PCE of6.41%.65 Stille polymerization was used to create a series of donor–acceptorcopolymers (25) containing a novel silafluorene unit coupled with thieno[3,4-c]-pyrrole-4,6-dione (PD), benzothiadiazole (BT), or diketopyrrolopyrrole (DPP) groups.BHJ solar cells were fabricated from PC61BM blends and ultimately performed with aPCE of 4.2% (Voc = 0.86 V, Jsc = 8.8 mA cm�2, FF = 56%). The absorption spectrumconfirmed a significant red-shift in silafluorene-containing polymer: PC61BM blendwhich indicates a high degree of planarisation for the copolymer. The side chains onSi centre improved the intercalation of PC61BM to favour high hole mobility.66


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Kumada polymerisation was used for the synthesis of a novel bithiophenylsilane-based dendritic polymer (26) with s–p-conjugation between bithiophene toterthiophene fragments. Spectral-luminescent characterisations indicate that thereis a non-radiative transfer of the electronic excitation energy from bithiophene toterthiophene fragments by an inductive resonance mechanism. The intramolecularenergy transfer efficiency for the polymer was measured to be 50%.67

A series of silole-containing poly(silylenevinylene)s (27; typical Mw = 95 300;PDI = 2.8) were synthesised by hydrosilylation using a Rh(PPh3)3Cl catalyst. FT-IR,multi-nuclear NMR and GPC were used to characterise the materials. In the thinfilm solid state, the polymers became significantly emissive implying thatthey have aggregation-enhanced emission characteristics. A superamplifi-cation effect useful for explosive detection was observed when the emission ofthe silole-polymers was quenched by picric acid. This trait therefore suggests thatthe silole polymer may be useful for the detection of trace compounds found inexplosives.68

Oligomeric poly(imide-amide)s (28) have been synthesised from bis(4-amino-phenyl)diphenylsilane various diacids derived from a-amino acids. UV-Vis spectrashowed that the addition of chiral, amide and imide groups increases polymerbackbone flexibility, which results in disruption of the extended p-conjugation.The four phenyl groups attached to Si also hinder planar configuration of thesystem and decreases the polymer conductivity.69

7. Polysiloxanes

Recently, a series of macrocyclic and linear co-oligocarbosiloxanes containingpendant ferrocenyl moieties were reported.70 Hydrosilylation of 1,3-dimethyl-1,3-diferrocenyl-1,3-divinyldisiloxane [(CH2QCH)(Fc)MeSi]2O with 1,1,3,3-tetra-methyldisiloxane formed the oligocarbosiloxane products (19) that were isolatedby chromatography and characterised by multinuclear (1H, 13C, 29Si) NMRspectroscopy, FT-IR, and matrix-assisted laser desorption/ionization (MALDI) –time-of-flight (TOF) mass spectrometry. The electrochemical properties studiedby cyclic and square wave (SQW) voltammetry demonstrated reversible two


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oxidation-steps which were indicative of strong electronic and electrostaticinteractions among the ferrocenyl groups.

Novel polysiloxane and polycarbosilane aerogels (20a, b) were recently synthesisedvia hydrosilylation of poly(hydromethylsiloxane) (PHMS) with 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (TMTV) in acetone and polycarbosilane (PCS)with 1,4-divinylbenzene (DVB) in cyclohexane (both were isolated by supercriticaldrying with CO2).71 A density as low as 0.17 g cm�3 and porosity of ca. 84 vol% wasreported for the polysiloxane aerogel. This is the first report of hydrosilylation usedfor crosslinking method in the synthesis of aerogels.

Polysiloxane polymers containing novel borate anion and cyclic carbonate sidechains were prepared by hydrosilylation of poly(hydromethylsiloxane) with vinyl-functionalized borates. The structure of the polymers was confirmed by multi-nuclear NMR and DSC. Introduction of a perfluorinated borate ionomer onto thepolysiloxane was shown to raise the ionic conductivity in spite of a relatively highTg (�16 1C). The challenge of lowering the Tg of borate containing polysiloxane tomaximise its conductivity still remains.72 A novel polysiloxane with CO2 – philicside chains has been produced by a three-step functionalisation of the hydro-silylation product of poly-(hydromethylsiloxane) and tert-butylacrylate. Hydrolysis ofester side-chains and conjugation with tert-butylamine afforded the correspondingamido polysiloxane which was readily chlorinated with tert-butylhypochlorite toproduce the final N-halamine polysiloxane (21). FT-IR and X-ray photoelectronspectroscopy (XPS) iodometric titration was used to characterise the cotton bearingthe material whereas biocidal capability was evaluated against Staphylococcus aureusand Escherichia coli.73

A series of hybridized poly(urethane-siloxane)s have been produced fromhydroxyl-functional aliphatic Boltorn hyperbranched polyesters. FT-IR, DSC anddynamic mechanic analysis (DMA) confirmed a,o-functionalisation of poly-dimethylsiloxane (PDMS) with the hyperbranched polyesters. TGA and hardnesstests indicated a lower thermal stability and higher hardness value for hybridmaterials created from an increasing pseudogeneration number for the hyper-branched polymer (HBP) starting material.74 A novel flame retardant was syn-thesised from coupling bisphenol A to hydro-functionalised polysiloxane usingstannous octate as a catalyst. The polymer, when mixed with polycarbonate to formcomposites, proved to be effective as a flame retardant as well as smoke suppressant.75

Other developments in this topic include the following. The demonstration of


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photoacid catalysed copolymerisation of 2,2,8,8-tetramethyl-1,7-dioxa-6-silaspiro-[5.5]undecane and a,o-dihydroxy-terminated PDMS was reported.76 Syntheticpathways of photo-induced cross-linking of poly(4-hydroxystyrene-block-styrene)and poly(4-tert-butoxystyrene-block-styrene) with the presence of siloxane cross-linker were also reported. The use of cyclic siloxane cross-linker can formstructures with a nanoparticle with surface olefins groups that allow for post-synthetic modification.77

8. Germanium-containing polymers

The synthesis of poly(germyl-s-indacene) and (germyl-s-indacene carbodiimides)(22) from organogermanium dichloride monomers was reported. The polycon-densation of the bis-chlorogermylindacenes with dilithiated s-indacene affordedthe organogermane polymer in sufficient yield for full characterisation by NMR,TGA, FT-IR and GPC (Mn = 2500–8000 and PDI = 2.08–2.16). Alternatively,dilithiated carbodiimide could be used to afford the poly(germyl-s-indacenecarbodiimide) (Mn = 2100–7000 and PDI = 1.17–1.31). A high thermal stabilitywas confirmed for these polymers with a main thermal degradation event in therange of 250–350 1C.78

Unique Si or Ge-containing poly(amide)s (23) were developed from the polymer-isation of bis(4-aminophenyl)diphenylsilane or bis(4-amino)diphenylgermanerespectively, via Yamazaki reaction. Multinuclear NMR, UV-Vis, Raman, TGA, andDSC (Tg = �64 and �60 1C, respectively) were used to characterise the polymers.Notably, the steric hindrance and lack of symmetry at the main chain with Si or Gecentres led to a decrease of the Tg value and a large optical band gap.79

9. Selenium and tellurium-containing polymers

Developments in selenium- and tellurium-containing polymers have occurred in2012. Excitingly, many of these polymers have shown promise in advanced applica-tions such as photovoltaics, memory devices, self-assembly and bio-conjugation. Atitanacyclopentadiene-based organometallic polymer (24) was synthesised from poly-condensation of titanium(IV) isopropoxide and ethynylbenzene. This polymer was alsofound to be a useful precursor for synthesising thiophene or selenophene-containingp-conjugated polymers via polycondensation reactions.80 The Stille-coupling polymeri-sation process was used to synthesise a dithienyl-diketopyrrolopyrrole polymer bearingsiloxane pendants and selenophene monomer. The Si- and Se-containing polymers


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(25) demonstrated high electron and hole mobility values of 2.20 and 3.97 cm2 V�1 s�1,respectively. The inorganic polymer’s siloxane-side chains were proposed to enhancecoplanarity and intermolecular interactions in the solid state and consequentlyimprove charge mobility in thin films.81

The Stille cross-coupling reaction was also used in another study to create a seriesof novel thiophene- and selenophene-based polymers containing quinoxaline anddiketopyrrolopyrrole as acceptors.82 The highest Jsc in the author’s series was 12.33mA cm�2 and their highest PCE from BHJ solar cells was reported as 3.18%. Anotherstudy also used Stille cross-coupling reaction to synthesise novel seleno[3,4-c]pyrrole-4,6-dione-based polymers with an optical bandgap of 1.84 eV and low PCE of0.28%.83 Copolymers with narrow band gaps as low as 1.41 eV have been synthesisedby Suzuki coupling reaction between 9,9-dioctylfluorene and 6,7-dimethyl-4,9-di(selenophene-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline.84 The LED devices fabri-cated from the polymers exhibited near-IR emission between 0.8 and 0.9 mm.

The nickel-catalysed chain-growth copolymerization of thiophene and seleno-phene derivatives was shown to produce p-conjugated copolymers (26) with atunable linear gradient sequence of incorporated monomers. Accordingly, it wasshown that adjusting the copolymer sequence permitted the tuning of the thin-film morphology, thermal and optical properties of the inorganic polymers.85

The group of Seferos has recently synthesised a series of D–A copolymers withcyclopentadithiophene as the donor monomer and benzochalcogenodiazole witheither S, Se, or Te as the acceptor monomer. The S-, Se-, and Te-containingpolymers (27a–c, respectively) were determined to have band gap values of 1.59,1.46, and 1.06 eV, respectively. Optical absorption spectroscopy revealed that theentire dual-band spectrum undergoes a bathochromic shift as the substitutedinorganic element becomes heavier. This implies that substituting heavy inor-ganic atoms into the acceptor monomer in such materials is a strategy forreducing the band gap in the inorganic polymers.86

A similar structure–property relationship study for a series of novel seleno-phene-based polymers containing bridging O or S substituents was conducted.The polyselenophenes (28a–e) were synthesised via electropolymerisation. The Satom bridge in the side chain was found to decrease the band gap and lower theHOMO level of the polymers while the O bridge gave greater backbone rigidity.87

Seferos et al.88 used Grignard metathesis polymerisation to synthesise a series ofP3HSe-co-P3HT copolymers with controlled Se content as well as molecular weights.Adjustment of the optical absorption was demonstrated by controlling the seleno-phene to thiophene ratio. The extent of order in self-assembled materials was observedto decrease as the P3HSe block became significantly longer than that of P3HT.


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Stille coupling polymerisation was used to perform biaxial extensions ofquarterthiophene–thiophene and –selenophene polymers (29). The resultingpolymers had reduced conformational distortion in the main chain and thereforeexhibited a reduced band gap. The polymer containing two selenophenes wasfound to have a high hole mobility (4.28 cm2 V�1 s�1) and consequently apromising power conversion efficiency (PCE) from its PC71BM blend-based BHJsolar cell (PCE = 2.60%).89 In similar work, selenopheno[3,4-b]selenopheneand benzodiselenophene were copolymerised and applied to fabricate a BHJsolar cell which gave PCE of 6.87% (30).90 Novel N,N0-bis(2-phenylethyl)erylene-3,4:9,10-tetracarboxylic diimide based poly[2,5-bis(4-aminophenylenesulfanyl)-selenophene/thiopene-hexafluoroisopropylidenediphthalimide] polymers wererecently synthesised for their application in organic field-effect transistor (OFET)devices.91

Atomic force microscopy (AFM)-based single-molecule force spectroscopy(SMFS) was used to investigate the effect of selenide oxidation to selenone onthe amphiphilicity of the novel selenium-containing amphilic block copolymer(PEG-PUSe-PEG).92 A series of poly(3-alkyltellurophene)s (31) have been synthe-sised by electrochemical oxidation and Kumada catalyst transfer polymerisation.The absorption spectra showed the polymers to be 93% regioregular with anarrow optical band gap of 1.57 eV.93 The synthesis of novel solution processedn-type polymer, poly(naphthalene-diimide-alt-biselenophene) (PNDIBS, 32) wasreported by the group of Jenekhe. The materials were found to have a very narrowoptical band gap of 1.4 eV making them excellent candidates for photovoltaics.94

A series of hyperbranched Se- or Te-containing polymers was synthesised andexhibited activity that mimics glutathione peroxidase (GPx) (33). The increase inthe polymer molecular weight and the degree of branching were found toenhance the GPx-like activity.95

A coordination responsive Se-containing block copolymer designed for thecontrolled release of doxorubicin was synthesised. The block copolymer formsmicelles in water when coordinated to Pt2+ but the competitive coordination withglutathione was found to uncoordinate Pt2+ therefore releasing doxorubicin.96


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10. Ferrocene-containing and related metallocenepolymers

The synthesis of amphiphilic A–B block and AB2 miktoarm star (34) copolymers ofpoly(vinylferrocene) (PVFc) was reported in 2012. The synthesis made use ofbenzyl glycidyl ether to afford hydroxyl-terminated PVFc that could be used toinitiate the ring-opening polymerisation of ethyleneoxide.97 The copolymers(AB copolymer: Mn = 10 000–48 000 and PDI = 1.06–1.12; AB2 copolymer; Mn =8000–40 000 and PDI = 1.10–1.25) were characterised by GPC, NMR, MALDI massspectroscopy and DSC. The iron-content proved sufficient for structural investiga-tions of solution self-assembly by transmission electron microscopy (TEM).Similarly, the anionic copolymerisation between ferrocenyl glycidyl ether (FcGE)and ethyleneoxide (EO) was established such that water-soluble thermorespon-sive ferrocenyl polymers could be isolated (Mn = 2100–8100, PDI = 1.07–1.20) (35).The materials were characterized by NMR, GPC, CV and UV-Vis spectroscopy. Thecytotoxicity of P(EO-co-FcGE) via cell viability test confirmed that copolymers witha high Fc concentration have a strongly cytotoxic behaviour.98

Surface-initiated atom transfer radical polymerisation (SI-ATRP) was used tosynthesise poly[2-(methacryloyloxy)ethylferrocenecarboxylate] (PFcMA) (36) brusheson cross-linked polystyrene particles. Quantification of the brush-content wasaccomplished by TGA and UV-Vis spectroscopy while dynamic light-scatteringmeasurements confirmed a linear relationship for the brush thickness with thehydrodynamic radius of the polymer. The brushed-particles were shown tobe redox-responsive by CV and DLS. Thermal conversion of the brush tosuperparamagnetic iron was confirmed by SQUID magnetisation experiments.99

The group of Manners has succeeded in metallating the cyclopentadienyl (Cp)rings of PFDMS (37) by employing Schlosser’s base pair in a lithiation reaction.The NMR studies indicated regioselectivity of the reaction occurring on theb-carbon of the Cp ring.100 The Manners group has recently investigated theredox activity of surface-relief gratings of polyferrocenylsilane block copolymers(38) bearing segment with complexed with ethyl orange ions. Photo-inducedsurface-relief gratings were found to be redox-active and permitted modulation ofthe grating depth from 50–85 nm.101

In other related work, the Manners group has demonstrated a hierarchicalassembly of self-assembled poly(ferrocenyldimethylsilane) (PFS)-based amphi-philic triblock co-micelles formed from PFS-block-poly(2-vinylpyridine) andPFS-block-PDMS (PFS-b-PDMS 39, PFS-b-P2VP 40). The triblock co-micelles can


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be tuned to form cylindrical [(I) in figure] or star-like [(II) in figure] micelles bycontrolling the degree of polymerisation of nonpolar and polar micellar blocks.102

Another study by group of Manners reported the synthesis of an amino-terminated PFS series that were useful for functionalisation with tetrapeptidegroups. Various tetrameric combinations of alanine, glycine and valine wereinstalled at the amino-terminus of the PFS and characterized by MALDI massspectroscopy, FT-IR and GPC (Mn = 3520–12 150, PDI = 1.21–1.35). The polymersself-assembled into anti-parallel b-sheet structures in the solid state and formedpeptidic-PFS core–coronae structures in solution.103

A novel donor–acceptor polymer (41) was synthesised from the unique Staudingerreaction between ferrocene derivative and 11,11,12,12-tetracyanoanthraquino-methane (TCNAQ). The polymer was characterised by multinuclear NMR, TGA,UV-Vis, CV, DSC (Tg = 227 1C) and GPC (Mn = 38 720; PDI = 53 670). The strong broadabsorption peak at 450–700 nm region of UV-Vis spectrum indicated the facilitationof intramolecular donor–acceptor charge transfer (ICT) by the phosphoraniminelinkage in the polymer.104 The band gap was estimated by both CV and UV-Vis andwas found to be 1.59 and 1.77 eV, respectively. A novel carbosilane metallo-dendrimers (42) with titanocene dichloride was synthesised via hydrosilylationreaction. Mass spectroscopy and multinuclear NMR confirmed the extent ofattachment of titanocene groups at all peripheral vinylsilane groups in thehydrosilylation step.105

A ring-opening polymerization (ROP) strategy has been used to preparepoly(ferrocenylalumane), poly(ruthenocenylalumane) and poly(ruthenocenylgallane)(Mw = 36 000–106 000, 8070 and 10 100–28 600, respectively). Multinuclear NMR, andDLS were used to confirm the polymerisation.106

11. Rare earth-containing and metal-porphyrin-basedpolymers

Recently, ring-opening metathesis polymerization (ROMP) was used to synthesiseIr(ppy)2(bpy) PF6 and PEG containing luminescent polymers which were found tohave enhanced quantum yield upon micellisation. The group also incorporatedbiotin in the monomer to ensure strong binding between the micelles andstreptavidin-coated magnetic beads.107

Pd-catalyzed Stille-coupling method was used to synthesise a series of donor–acceptor copolymers (43) based on carbazole and quinoxalinoporphyrin with varyingthiophene p-bridges in between. NMR, UV-Vis, photoluminescence spectroscopy,


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CV, TGA, DSC and GPC (Mn = 3400–66 400; PDI = 1.42–2.13) were used tocharacterise the polymers. The bulk heterojunction photovoltaic devices fabri-cated from these polymers highlighted the significance of the p-bridge on the PCEof the device. The presence of Zn ion in porphyrin (POR) ring enhanced the holemobility but compromised the PCE due to disadvantageous morphology forexciton dissociation.108

Sonogashira coupling been employed in the synthesis of n-type conjugatedpolymers (44) with main chain azadipyromethene (aza-DIPY) dyes capable ofborane, Cu(I) and Ag(I) loading. The boron-, copper- and silver-containing poly-mers were characterised by NMR, TGA, UV-Vis, CV, X-ray diffraction and GPC(Mn = 5000–15 300 and PDI = 1.8–2.3; Mn = 6900 and PDI = 3.5; Mn = 6900 andPDI = 3.6, respectively). The electron deficient –BF2 functionalised polymerexhibited lowered HOMO and LUMO levels while the Cu(I) and Ag(I) derivativesshowed marginally raised HOMO–LUMO levels.109

A series of Pt-containing organometallic polyaniline with benzoquinone and1,4-diaminobenzene spacers was reported.110 Another novel polymetallayne wasirradiated by increasing doses of gamma rays and detected chlorine and hydrogenradicals generations due to the radiolysis.111 Novel Cu(I) coordinated polymer wassynthesised through the aqueous subcomponent self-assembly reaction between2,9-diformyl-1,10-phenan-throline and diamine C with Cu(I). This is the first whitelight emitting electrochemical cells composed of ionic transition-metal complexes.112

Novel donor–acceptor copolymers (45) made from dithienocoronene (DTCDI) andZn porphyrin accepting and donating planar units was reported. The Zn-containingcopolymer displayed good solubility in common organic solvents to lend itself toseveral characterisation methods including NMR, UV-Vis, TGA, CV, GPC (Mn = 21 400and PDI = 3.69). Excellent thermal stability was reported with an onset for thermaldecomposition at a temperature of 323 1C. UV-Vis spectra showed higher degree ofelectron delocalization due to the presence of large and planar DTCDI and also thedonor-to-acceptor charge-transfer at 722 nm. The conjugation, planarity, and rigidityenhanced by DTCDI unit was also demonstrated with a two-photon absorptionexperiment.113 Recently, a novel fluorine-bridged benzimidazolium salt (BNM) wasprepared and its direct complexation reaction with PdCl2 or PtCl2 was performed tosynthesise new organometallic polymers (Mn = 7600 and PDI = 1.35; Mn = 8100 andPDI = 1.30, respectively) (46). CV revealed that although the LUMO levels of PMPd


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and PMPt increased upon metallation, the HOMO level of the polymers were nearlyidentical to that of unmetallated BNM. The absorption and photoluminescence (PL)spectra showed that the metal–benzylbenzimidazoyl coordination did not extend theconjugation.114

Interesting Re- and Pt-containing polymers (47) have been synthesised by thefunctionalisation of bithiazole-containing polyplatinynes with ReCl(CO)5 (Mn =9220–19 810 and PDI = 1.84–2.92). GPC, multinuclear NMR, FT-IR, UV-Vis, CV andphotoluminescence emission spectroscopy were used for characterisation wherethe latter showed that the bandgaps of the Pt(II) complex polymers can becontrolled between the range of 2.18 to 1.85 eV by modifying the length ofoligothiophene chain length (m) as well as by complexation with Re(CO)5.115

A novel Ru-containing polymer (48) based on bidentate N4N ligands weresynthesized via still cross-coupling reaction. Multinuclear NMR, UV-Vis, FT-IR, CVand TGA were used to confirm the structure. The modification of substituent groupsof the ancillary ligands (R) altered the absorption properties of the polymers andtherefore represents an attractive method for tuning the bandgap of the organo-metallic polymers.116 Novel zinc-containing D–A polymers (49) were synthesised via aStille coupling of benzodithiophenes and a dimethyl triphenylamine-functionalizedZn-POR monomers and subsequently characterized by MALDI, UV-Vis, PL spectro-scopy, TGA, CV and GPC (Mn = 4100 and PDI = 1.38). The PL spectra exhibited broadabsorption in the 300–650 nm regions while CV showed a reduction in the LUMOenergy level occurs upon introduction of an electron-deficient dithiophenylbenzothia-diazole thiophene adjacent to the benzodithiophene units in the main chain.117

Similarly, novel alternating D–A copolymers (50) were synthesised by step-growthpolymerisation using the Sonogashira cross-coupling reaction between POR dialynesand diiodoaryl monomers (Mn = 25 800–61 700; PDI = 1.18–1.31). Owing to the doubly-strapped porphyrin linkages in the polymer backbone, these copolymers exhibitorthogonally and alternately arrayed transition dipoles. Full characterisation by NMR,UV-Vis, and fluorescence spectroscopy confirmed the structure. The fluorescenceresonance energy transfer (FRET) study on these copolymers demonstrated a newFRET system based on the arrangement of dipoles in this polymer.118

Novel conjugated Pt- and Ir-containing polymers (51) have been synthesised byHagihara coupling. NMR, and GPC confirmed the oligomeric structure of the materials.Optical absorption and emission spectroscopy corroborated with density functionaltheory calculations that confirmed that the presence of luminescent cationic Ir acceptormoiety allows for charge transfer transitions between the Pt and Ir units.119

The group of Lin has utilised a Pd/CuI-catalyzed Sonogashira cross-couplingreaction between the tetrahedral tetra(p-ethynylphenyl)-methane and dibrominated[Ru(bpy)2-(dbbpy)]2+ or Ir[(bpy)2(dbbpy)]+ to synthesise novel Ru- or Ir-containing


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polymers (52). The polymers were found to be thermally stable up to 300 1C andhave particle-like structure with a diameter of 100–200 nm. An efficient core-to-surface transport of the excited-state was verified through quenching experi-ments. Accordingly, the materials were effective photocatalysts for aza-Henryreactions.120 The Suzuki polycondensation was used to synthesise a series ofhyperbranched copolymers with carbazole-3,6-diyl-co-2,8-dioctyldibenzothiophene-S,S-dioxide-3,7-diyl as the branch and Ir(ppy)3 as the core (53).121

Another study by the group of Harvey reported the synthesis of diethynyl-[2.2]paracyclophane (PCP)-containing organometallic polymers (54). The absorp-tion values for polymers 54a–c were 315, 360, and 420 nm; phosphorescenceemission spectra were 530, 505, and 645 nm, respectively. The rates of triplet energytransfers found in these polymers led to the conclusion that PCP does not affect theelectronic communication in conjugated chains.122

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