New π‐Conjugated polymers containing 4H,4′H‐[1,1′‐Bithieno [3,4‐C]Pyrrole]‐4,4′,6,6′(5H,5′H)‐Tetraone (biTPD) units and their application to thin‐Film transistors and photovoltaic cells

We successfully synthesized new D‐A copolymers that employ 1,10‐bithienopyrrolodione (biTPD), thiophene, and selenophene‐based donor monomeric units. Two polymers, PBTPDEBT and PBTPDEBS , exhibited high degrees of crystallinity and unique polymer chain arrangements on the substrate, which is attributed to their enhanced coplanarity and intermolecular interactions between the polymer chains. Among the thin‐film transistor devices made of PBTPDEBT and PBTPDEBS , the annealed PBTPDEBS device displayed relatively high hole mobility, which was twice that of the PBTPDEBT ‐based device. In addition, an organic photovoltaic device based on a PBTPDEBS :PC₇₁BM blend displayed the maximum power conversion efficiency of 3.85%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1228–1235     

Synthesis of comb‐type polycarbosilanes via nucleophilic substitution reactions on the main‐chain silicon atoms

A series of comb‐type polycarbosilanes of the type [Si(CH₃)(OR)CH₂]_n {where R = (CH₂)_mR′, R′ = ? O‐p‐biphenyl? X [X = H (m = 3, 6, 8, or 11) or CN (m = 11)], and R′ = (CF₂)₇CF₃ (m = 4)} were prepared from poly(chloromethylsilylenemethylene) by reactions with the respective hydroxy‐terminated side chains in the presence of triethylamine. The product side‐chain polymers were typically greater than 90% substituted and, for R′ = ? O‐p‐biphenyl? X derivatives, they exhibited phase transitions between 27 and 150 °C involving both crystalline and liquid‐crystalline phases. The introduction of the polar p‐CN substituent to the biphenyl mesogen resulted in a substantial increase in both the isotropization temperature and the liquid‐crystalline phase range with respect to the corresponding unsubstituted biphenyl derivative. For R = (CH₂)₁₁? O‐biphenyl side chains, an analogous side‐chain liquid‐crystalline (SCLC) polysiloxane derivative of the type [Si(CH₃)(O(CH₂)₁₁? O‐biphenyl)O]_n was prepared by means of a catalytic dehydrogenation reaction. In contrast to the polycarbosilane bearing the same side chain, this polymer did not exhibit any liquid‐crystalline phases but melted directly from a crystalline phase to an isotropic liquid at 94 °C. Similar behavior was observed for the polycarbosilane with a fluorocarbon chain, for which a single transition from a crystalline phase to an isotropic liquid was observed at ?0.7 °C. The molecular structures of these polymers were characterized by means of gel permeation chromatography and high‐resolution NMR studies, and the crystalline and liquid‐crystalline phases of the SCLC polymers were identified by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 984–997, 2003     

Pyrrolo[3,4‐c]pyrrole‐1,3‐dione‐based large band gap polymers containing benzodithiophene derivatives for highly efficient simple structured polymer solar cells

Pyrrolo[3,4‐c]pyrrole‐1,3(2H,5H)‐dione (DPPD)‐based large band gap polymers, P(BDT‐TDPPDT) and P(BDTT‐TDPPDT), are prepared by copolymerizing electron‐rich 4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene (BDT) or 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDTT) unit with novel electron deficient 2,5‐dioctyl‐4,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,3(2H,5H)‐dione (TDPPDT) unit. The absorption bands of polymers P(BDT‐TDPPDT) and P(BDTT‐TDPPDT) cover the region from 300 to 600 nm with an optical band gap of 2.11 eV and 2.04 eV, respectively. The electrochemical study illustrates that the highest occupied/lowest unoccupied molecular orbital energy levels of P(BDT‐TDPPDT) and P(BDTT‐TDPPDT) are ?5.39 eV/?3.28 eV and ?5.44 eV/?3.40 eV, respectively. The single layer polymer solar cell (PSC) fabricated with a device structure of ITO/PEDOT:PSS/P(BDT‐TDPPDT) or P(BDTT‐TDPPDT):PC70BM+DIO/Al offers a maximum power conversion efficiency (PCE) of 6.74% and 6.57%, respectively. The high photovoltaic parameters such as fill factor (～72%), open circuit voltage (V_oc, ～0.90 V), incident photon to collected electron efficiency (～76%), and PCE obtained for the PSCs made from polymers P(BDT‐TDPPDT) and P(BDTT‐TDPPDT) make them as promising large band gap polymeric candidates for PSC application. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3564–3574     

Chain‐growth condensation polymerization approach to synthesis of well‐defined polybenzoxazole: Importance of higher reactivity of 3‐amino‐4‐hydroxybenzoic acid ester compared to 4‐amino‐3‐hydroxybenzoic acid ester

Application of chain‐growth condensation polymerization (CGCP) to obtain well‐defined polybenzoxazole (PBO) was examined. CGCP of both phenyl 3‐{(2‐methoxyethoxy)methoxy (MEM‐oxy)}‐4‐(octylamino)benzoate ( 1b ) (para‐substituted monomer) and phenyl 4‐MEM‐oxy‐3‐(octylamino)benzoate ( 3b ) (meta‐substituted monomer) was examined in the presence of metal disilazide base and phenyl 4‐nitro‐ or methylbenzoate 2 as an initiator. Polymerization of the latter monomer, but not the former, afforded polymer with controlled molecular weight based on the feed ratio of monomer to initiator and with a narrow molecular weight distribution. Accordingly, monomer 3c , in which the octyl group on the amino nitrogen of 3b was replaced with a 4‐(octyloxy)benzyl (OOB) group, was polymerized in the presence of lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS), phenyl 4‐methylbenzoate ( 2b ), and LiCl in THF at 0 °C to yield poly 3c with well‐defined molecular weight (M_n = 4520–9080) and low polydispersity (M_w/M_n ≤ 1.11). Treatment of poly 3c with trifluoroacetic acid simultaneously removed the MEM and OOB groups, affording poly(o‐hydroxyamide) (poly 4 ) without scission of the amide linkages. Cyclodehydration of poly 4 proceeded at 350 °C to yield PBO (poly 5 ), which was insoluble in organic solvents and acids. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1730–1736     

Mixed‐valence class I transition and electrochemistry of bis(triphenylamine)‐based aramids containing isolated ether‐linkage

A series of solution‐processable electrochromic (EC) aromatic polyamides with bis(triphenylamine)ether (TPAO) units in the backbone were prepared by the phosphorylation polyamidation from a newly synthesized diamine monomer, bis(N‐4‐aminophenyl‐N‐4‐methoxyphenyl‐4‐aminophenyl)ether, and various dicarboxylic acids. These polymers were highly soluble in many organic solvents and showed useful levels of thermal stability associated with high glass‐transition temperatures and high char yields (higher than 50 at 800 °C in nitrogen). The polymer films showed reversible electrochemical oxidation and electrochromism with high contrast ratio in the visible range, which also exhibited moderate coloration efficiency (CE), low switching time, and good stability. Especially, the polyamides with two electroactive nitrogen centers only showed one‐stage oxidative coloring (no intervalence charge‐transfer [IV‐CT] band was detected), implying the two electrons are simultaneously removed from the TPAO units on account of the ether‐linkage definitely isolated the two redox centers. The mixed‐valence (MV) Class I/II/III transition and electrochemistry of the synthesized model compounds were investigated for the bridged triarylamine system with various N? N distances and intramolecular electron transfer (ET) capability. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Thermal stability of a star‐shaped poly(1,3‐cyclohexadiene)

A star‐shaped poly(1,3‐cyclohexadiene) (PCHD) with a fullerene‐C₆₀ (C₆₀) core (C₆₀‐PCHD) was prepared to examine the thermal stability of the covalent bond between the C₆₀ and PCHD arm in the C₆₀‐PCHD. The covalent bond between the C₆₀ and PCHD arm formed by a 1,2‐cyclohexadiene (CHD) unit on the C₆₀ was stronger than that formed by a 1,4‐CHD unit. The double bond in the CHD unit adjoining the C₆₀ core was a key structure for the stability of that covalent bond. The hydrogenated C₆₀‐PCHD, which did not contain a double bond, possessed significantly higher thermal stability compared to C₆₀‐PCHD. The mechanism of elimination of PCHD arm molecules from the C₆₀ core was thought to proceed via a 1,5‐sigmatropic H‐shift. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2132–2142, 2009     

Polyaddition of bifunctional 1,3‐benzoxazine and 2‐methylresorcinol

A polyaddition system consisted of a bifunctional N‐n‐propyl benzoxazine and 2‐methylresorcinol ( MR ) that proceeds at ambient temperature has been developed. In this system, the aromatic ring of MR acted as a bifunctional monomer, reacting with a two equivalent amount of benzoxazine moieties via their ring‐opening reaction. The polyaddition gave the corresponding linear polymer bearing phenolic moieties bridged by Mannich‐type linkage in the main chain. The linear polymer had a high glass transition temperature, which was comparable to that of the linear polybenzoxazine synthesized by the ring‐opening polymerization of a monofunctional N‐n‐propyl benzoxazine. The employment of a bifunctional N‐allyl benzoxazine in the polyaddition system resulted in the formation of the corresponding polymer with allyl pendants, which exhibited improved heat resistance due to its thermally induced crosslinking reaction. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3867–3872     

Synthesis and characterization of novel soluble triphenylamine‐containing aromatic polyamides based on N,N′‐bis(4‐aminophenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine, N, N′‐bis(4‐aminophenyl)‐N, N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 4‐fluoronitrobenzene, followed by catalytic reduction. A series of novel aromatic polyamides with triphenylamine units were prepared from the diamine and various aromatic dicarboxylic acids or their diacid chlorides via the direct phosphorylation polycondensation or low‐temperature solution polycondensation. All the polyamides were amorphous and readily soluble in many organic solvents such as N, N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with relatively high glass‐transition temperatures (257–287 °C), 10% weight‐loss temperatures in excess of 550 °C, and char yields at 800 °C in nitrogen higher than 72%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2810–2818, 2002     

Poly(1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole‐alt−3,6‐carbazole/2,7‐fluorene) as high‐performance two‐photon dyes

This article reports the synthesis, one‐ and two‐photon absorption, and excited fluorescence properties of poly(1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole‐alt‐N‐octyl‐3,6‐carbazole/2,7‐fluorene) ( PDCZ / PDFL ). PDCZ and PDFL are synthesized by the Suzuki cross‐coupling of 2,5‐dioctyl‐1,4‐diketo‐3,6‐bis(p‐bromophenylpyrrolo[3,4‐c]pyrrole and N‐octyl‐3,6‐bis(3,3‐dimethyl‐1,3,2‐dioxaborolan‐2‐yl)carbazole or 2,7‐bis(3,3‐dimethyl‐1,3,2‐dioxaborolan‐2‐yl)fluorene and have number‐average molecular weights of 8.5 × 10³ and 1.14 × 10⁴ g/mol and polydispersities of 2.06 and 1.83, respectively. They are highly soluble in common organic solvents and emit strong orange one‐ and two‐photon excited fluorescence (2PEF) in THF solution and exhibit high light and heat stability. The maximal two‐photon absorption cross‐sections (δ) measured in THF solution by the 2PEF method using femtosecond laser pulses are 970 and 900 GM per repeating unit for PDCZ and PDFL , respectively. These 1,4‐diketo‐pyrrolo[3,4‐c]pyrrole‐containing polymers with full aromatic structure and large δ will be promising high‐performance 2PA dyes applicable in two‐photon science and technology. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 944–951     

Aromatic Ring‐Fused Carborane‐Based Luminescent π‐Conjugated Polymers

A series of π‐conjugated polymers linked by benzocarborane (1,2‐(buta‐1′,3′‐diene‐1′,4′‐diyl)‐1,2‐dicarbadodecaborane) were synthesized via Sonogashira–Hagihara polycondensation reaction. The opened molecular structure of diiodo monomer containing benzocarborane resulted in fast polymerization and high molecular weights. The obtained polymers were fully characterized by ¹H, ¹³C, and ¹¹B NMR spectroscopies. UV‐vis absorption and photoluminescence studies revealed the acceptor‐profile of benzocarborane. Unlike the polymers linked by o‐carborane, these polymers exhibited strong luminescence in the solution state, presumably because the inductive effect of carborane is dominant, rather than cage‐π interactions.

     

Thermally stable,light‐emitting,triphenylamine‐containing poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s bearing pendent carbazolyl groups

A series of new organosoluble poly(amine hydrazide)s were synthesized via the Yamazaki phosphorylation reaction and were solution‐cast into transparent films. Differential scanning calorimetry indicated that the hydrazide polymers could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(amine‐1,3,4‐oxadiazole)s exhibited glass‐transition temperatures in the range of 276–297 °C, 10% weight loss temperatures in excess of 520 °C, and char yields at 800 °C in nitrogen higher than 67%. The hole‐transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of these polymers prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidative redox couples at 1.10–1.19 and 1.35–1.60 V versus Ag/AgCl in an acetonitrile solution, respectively. The poly(amine hydrazide)s revealed excellent stability of the electrochromic characteristics, changing color from the original pale yellow to green and then to blue. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 48–58, 2007     

Blue‐light‐emitting and anodically electrochromic materials of new wholly aromatic polyamides derived from the high‐efficiency chromophore 4,4′‐dicarboxy‐4″‐methyltriphenylamine

A series of organosoluble, aromatic polyamides were synthesized from a 4‐methyl‐substituted, triphenylamine‐containing, aromatic diacid monomer, 4,4′‐dicarboxy‐4″‐methyltriphenylamine, which is a blue‐light (454‐nm) emitter with a fluorescence quantum efficiency of 46%. These triphenylamine‐based, high‐performance polymers had strong fluorescence emissions in the blue region with high quantum yields up to 64% and one reversible oxidation redox couple around 1.20 V versus Ag/AgCl in acetonitrile solutions. They exhibited good thermal stability, with 10% weight loss temperatures above 480 °C under a nitrogen atmosphere and with relatively high glass‐transition temperatures (252–309 °C). All the polyamides revealed excellent stability of electrochromic characteristics, changing color from the original pale yellow to blue. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4095–4107, 2006     

Dehydrogenation of poly(1,3‐cyclohexadiene)–polystyrene binary block copolymers

The dehydrogenation of poly(1,3‐cyclohexadiene)–polystyrene binary block copolymers obtained by anionic copolymerization with alkyllithium/amine systems was investigated for the first time. The dehydrogenation of the poly(1,3‐cyclohexadiene) block, which was composed of 1,2‐cyclohexadiene (1,2‐CHD) and 1,4‐cyclohexadiene (1,4‐CHD) units, was strongly affected by the polymer chain structure. The existence of 1,2‐CHD units prevented the dehydrogenation of the poly(1,3‐cyclohexadiene) block in the binary block copolymer. The rate of dehydrogenation was fast on a long sequence of 1,4‐CHD units, whereas it was relatively slow for 1,2‐CHD/1,4‐CHD (≈1/1) unit sequences. The bonding of the polystyrene block to the polymer chain effectively improved not only the rate of dehydrogenation of a long sequence of 1,4‐CHD units but also that of the polymer chain with a high content of 1,2‐CHD units. The dehydrogenation of a poly(1,3‐cyclohexadiene) block containing a small number of 1,2‐CHD units progressed via step‐by‐step reactions. The dehydrogenation of a long sequence of 1,4‐CHD units proceeded as the first step. Subsequently, in the second step, the 1,2‐CHD/1,4‐CHD (≈1/1) unit sequences remaining in the polymer chain were dehydrogenated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3526–3537, 2006     

Mechanism and characterization of alkylene‐ and p‐ethylenebenzylene‐spaced polycarbosilanes ceramic precursor synthesized by electropolymerization

An electropolymerization of haloalkylhalosilanes (Cl? R? SiCH₃Cl₂) that possess two types of electroactive sites, that is, the C? Cl and Si? Cl bond is described. The one‐pot synthesis method is shown to yield branched polycarbosilanes having a regular carbon block‐spaced silicon backbone structure. A series of branched polycarbosilanes, [? R? SiCH₃? ]_n with R being ? CH₂? , ? C₂H₄? , ? C₃H₆? , and ? CH₂? C₆H₄? C₂H₄? , have been successfully electropolymerized with M_n up to 42,600 Dalton. Experimental and simulation cyclic voltammetry of these monomers and the computational examination of their LUMOs are applied to study the electropolymerization mechanism. The results suggest that polymerization proceeds by iterating steps involving (1) electroreduction of a C? Cl bond to a carbanion, which is catalyzed by silylanion radical [Cl SiCl(CH₃)RCl] and/or Ni(0)/TDA‐1; and (2) nucleophilic attack of carbanions to Si? Cl bonds of a second monomer or oligomer to extend the polymer chain. The investigation reveals that the R spacer has a considerable impact on the polymerizability of the corresponding monomer. Such interfacial polymerization resembles a template polymerization, leading to unique microstructures that were preserved even after converted to silicon carbide ceramics at high temperatures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7677–7689, 2008     

Novel thermally stable triarylamine‐containing aromatic polyamides bearing anthrylamine chromophores for highly efficient green‐light‐emitting materials

A series of novel polyamides with pendent anthrylamine units were prepared via the direct phosphorylation polycondensation from various diamines and the anthrylamine‐based aromatic dicarboxylic acid, 9‐[N,N‐di(4‐carboxyphenyl)amino]anthracene (4). The aromatic polyamides had useful levels of thermal stability associated with relatively high softening temperatures (T_s) (290–300 °C), 10% weight‐loss temperatures (T_d¹⁰) nearly in excess of 550 °C, and char yields at 800 °C in nitrogen higher than 60%. These aromatic polyamides I exhibited highly photoluminescence quantum yield in NMP solution ranges from 55% for Ia to 74% for Ie due to the introduction of anthrylamine chromophores. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited one oxidation and reduction couples (E_onset) around 1.10 and ?1.50 V versus Ag/AgCl in acetonitrile (CH₃CN) and DMF solutions, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7354–7368, 2008     

Recent advances in the syntheses of radical‐containing macromolecules

Tailor‐made polymers containing specific chemical functionalities have ushered in a number of emerging fields in polymer science. In most of these next‐generation applications the focus of the community has centered upon closed‐shell macromolecules. Conversely, macromolecules containing stable radical sites have been less studied despite the promise of this evolving class of polymers. In particular, radical‐containing macromolecules have shown great potential in magnetic, energy storage, and biomedical applications. Here, the progress regarding the syntheses of open‐shell containing polymers are reviewed in two distinct subclasses. In the first, the syntheses of radical polymers (i.e., materials composed of non‐conjugated macromolecular backbones and with open‐shell units present on the polymer pendant sites) are described. In the second, polyradical (i.e., macromolecules containing stabilized radical sites either within the macromolecular backbone or those containing radical sites that are stabilized through a large degree of conjugation) synthetic schemes are presented. Thus, the state‐of‐the‐art in open‐shell macromolecular syntheses will be reported and future means by which to advance the current archetype will be discussed. By detailing the synthetic pathways possible for, and the inherent synthetic limitations of, the creation of these functional polymers, the community will be able to extend the bounds of the radical‐containing macromolecular paradigm. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1875–1894     

A novel benzimidazole‐containing phthalonitrile monomer with unique polymerization behavior

A novel benzimidazole‐containing phthalonitrile monomer (BIPN) was synthesized. The chemical structure of BIPN was confirmed by various spectroscopic techniques. Differential scanning calorimetry measurement revealed that the self‐promoted polymerization reaction of the BIPN proceeds extremely sluggish and showed low polymerization exothermic effect. Subsequent rheological measurement displayed that the BIPN was able to keep a stable and low melt viscosity for 4 h at 300 °C, 2 h at 310 °C, and 50 min at 330 °C. The derived BIPN polymers showed excellent thermal properties revealed by thermogravimetric analysis, which were better than those of the corresponding polymer derived from phthalonitrile monomer without benzimidazole moiety. IR analysis confirmed the occurrence of the triazine ring within the polymer crosslinking sites. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Reduced‐bandgap triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene copolymers pending benzothiadiazole or diketopyrrolopyrrole units for efficient polymer solar cells

Two new side‐chain donor–acceptor (D‐A)‐based triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene (TPA‐alt‐BDT) copolymers ( P1 and P2 ) with pendant benzothiadiazole (BT)/diketopyrrolopyrrole (DPP) in TPA unit were synthesized by Stille coupling polymerization. Their thermal, photophysical, electrochemical, blend film morphology and photovoltaic properties were investigated. Efficient bulk heterojunction polymer solar cells (PSCs) were obtained by solution process using both copolymers as donor materials and PC₇₁BM as acceptor. The maximum power conversion efficiency (PCE) of 3.17% with a highest open‐circuit voltage (V_oc) of 0.86V was observed in the P1 ‐based PSCs, while the maximum short‐circuit current (J_sc) of 10.77 mA cm^?2 was exhibited in the P2 ‐based PSCs under the illumination of AM 1.5, 100 mW cm^?2. The alternating binary donor units and pending acceptor groups played a significant role in tuning photovoltaic properties for this class of the side‐chain D–A‐based copolymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4103–4110     

Synthesis of star poly(1,3‐cyclohexadiene): Grafting reaction of poly(1,3‐cyclohexadienyl)lithium onto C60

The grafting reaction of poly(1,3‐cyclohexadienyl)lithium onto fullerene‐C₆₀ (C₆₀) was strongly affected by the nucleophilicity of poly(1,3‐cyclohexadiene) (PCHD) carbanions and the polymer chain microstructure, and progressed via step‐by‐step reactions. A star‐shaped PCHD, having a maximum of four arms, was obtained from poly(1,3‐cyclohexadienyl)lithium composed of all 1,4‐cyclohexadiene (1,4‐CHD) units. The rate of the grafting reaction was accelerated by the addition of amine. The grafting density of PCHD arms onto C₆₀ decreased with an increase in the molar ratio of 1,2‐cyclohexadiene (1,2‐CHD) units. The electron‐transfer reaction from PCHD carbanions to C₆₀ did not occur in either a nonpolar solvent or a polar solvent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3282–3293, 2008.     

Amphiphilic Hybrid π‐Conjugated Polymers Containing Polyhedral Oligomeric Silsesquioxanes

Amphiphilic hybrid π‐conjugated polymers that have polyhedral oligomeric silsesquioxanes on their side chains have been successfully synthesized by the Sonogashira–Hagihara polycondensation reaction. The obtained polymers were studied with ultraviolet‐visible absorption and photoluminescence spectra. In these polymers, the π‐conjugation length was extended along the poly(p‐phenylene‐ethynylene) backbone. Furthermore, the content of the POSS substituents can influence the aggregation behavior of the polymers and subsequent luminescent properties.