Solution route to inorganic nanobelt‐conducting organic polymer core‐shell nanocomposites

A facile and versatile solution‐based approach was developed to prepare semiconductor metal oxide nanobelt‐conducting organic polymer core‐shell nanocomposites. Well‐defined nanobelts of several types of oxide nanobelts were combined with conducting polymer [polypyrrole (PPy) and polyaniline (PANi)] via in situ polymerization in aqueous solution to obtain a new type of inorganic–organic composite nanostructure. Samples were characterized by using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, electron energy loss spectra, high‐resolution transmission electron microscopy, and ultraviolet–visible techniques. Electron energy loss spectra revealed the existence of C?C and C? N bonds in coating layers to prove the encapsulation of PPy or PANi. The red‐shift of absorption band at high‐energy was observed for PPy‐encapsulated composites via ultraviolet–visible spectroscopy, and significant absorption band shifts were also encountered to PANi‐encapsulated composites, which suggest possibilities of band‐gap tuning of such metal oxide‐conducting polymer composites to be applied especially in solar cell devices. However, the sacrifice of nanobelts‐core led to hollow structures of PPy and PANi, which expands the synthetic strategies to prepare conducting polymer nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2892–2900, 2005     

Tuning the optical properties of hyperbranched polymers through the modification of the end groups

Dye‐capped, hyperbranched, conjugated polymers were prepared by the modification of the peripheral bromo end groups of the hyperbranched polymer core with a palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction. The dye‐modified, hyperbranched polymers had high molecular weights and displayed good solubility in common organic solvents such as tetrahydrofuran, toluene, and chloroform. The structure of the dye‐modified, hyperbranched polymers was characterized by ¹H and ¹³C NMR and elemental analysis. The thermal properties of five kinds of hyperbranched polymers were investigated with thermogravimetric analysis and differential scanning calorimetry. The optical properties of the dye‐capped, hyperbranched polymers were investigated with ultraviolet‐absorption and fluorescence spectroscopy. The hyperbranched structure could effectively reduce the aggregation of the peripheral dyes. The emission colors of the hyperbranched polymers could be easily tuned by end‐group modification. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 111–124, 2007     

Light absorption due to higher harmonics of molecular vibrations in transparent amorphous polymers for plastic optical fibers

We have studied simple empirical equations to estimate light absorption loss α_v due to harmonics of molecular vibrations of transparent amorphous polymers used in plastic optical fibers (POFs). In the visible region, absorption involves two losses. One is α_v, and the other is the electronic transition absorption loss, α_e. Of the two, α_v is considerably larger than α_e in the wavelength region used for optical communication with POFs. We have clarified relationships between chemical structure of repeat units of polymers and α_v. We find that α_v is proportional to the concentration of specific chemical bonds (C? H, N? H, and Obond;H bonds) in the polymer solid, and we propose empirical equations to estimate α_v from the polymer density and the chemical structure of the repeat unit. These equations are used to estimate α_v of several polymers [i.e., poly(methyl methacrylate), polystyrene, and polycarbonate]. The estimated values are nearly equal to the experimental or reference values. Furthermore, to minimize the attenuation in the POF, we conclude that the POF core polymer should have no N? H, O? H, or aliphatic C? H bonds in its repeat unit.     

Controlled synthesis and chemical modification of unsaturated aliphatic (Co)polyesters based on 6,7‐dihydro‐2(3H)‐oxepinone

A pure unsaturated cyclic ester, 6,7‐dihydro‐2(3H)‐oxepinone (DHO2), was prepared by a new synthetic route. The copolymerization of DHO2 with ?‐caprolactone (?CL) was initiated by aluminum isopropoxide [Al(OⁱPr)₃] at 0 °C as an easy way to produce unsaturated aliphatic polyesters with nonconjugated C?C double bonds in a controlled manner. The chain growth was living, as certified by the agreement between the experimental molecular weight at total monomer conversion and the value predicted from the initial monomer/initiator molar ratio. The polydispersity was reasonably low (weight‐average molecular weight/number‐average molecular weight ≤ 1.2). The homopolymerization of DHO2 was, however, not controlled because of fast intramolecular transesterification. Copolymers of DHO2 and ?CL were quantitatively oxidized with the formation of epoxides containing chains. The extent of the epoxidation allowed the thermal properties and thermal stability of the copolyesters to be modulated. The epoxidized copolyesters were successfully converted into thioaminated chains, which were then quaternized into polycations. No degradation occurred during the chemical modification. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2286–2297, 2002     

Anthracene‐containing conjugated polymer showing four optical transitions upon doping: A spectroscopic study

An anthracene‐containing poly(arylene‐ethynylene)‐alt‐poly(arylene‐vinylene) (PAE‐PAV) of general constitutional unit (? Ph? C?C? Anthr? C?C? Ph? CH?CH? Anthr? CH?CH)_n bearing two 2‐ethylhexyloxy solubilizing side chains on each phenylene (Ph) unit has been synthesized and characterized. The basic electrochemical characterization was done, showing the existence of two non‐reversible oxidation and one reversible reduction peaks. The optical properties, the real and imaginary part of the dielectric function, were probed using spectroscopic ellipsometry (SE). The vibrational structure of the undoped/doped polymer was investigated using Fourier transformed infrared spectroscopy. A strong change in the polaronic absorption was observed during the doping, which after modeling revealed the existence of two separated transitions. The optical changes upon doping were additionally recorded using the SE technique. Similar to the results from FT‐IR spectroscopy, two new in‐the‐gap absorptions were found. Moreover, the electrical conductivity as well as the mobility of positive carriers were measured. In the undoped state, the conductivity of the polymer was found to be below the detection limit (<μS cm^?1), after doping the conductivity increased to 0.69 S cm^?1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 338–346     

New reaction for the preparation of liquid rubber

The article reports on the noncatalytic transformation of a polybutadiene (number‐average molecular weight = 128,000) into a functionalized liquid rubber via the carboxidation of the polymer C?C bonds by nitrous oxide. The reaction was conducted in a benzene solution at 160–230 °C and a pressure of 3–6 MPa. The carboxidation mechanism was determined. The main route (95%) of the reaction proceeded without cleavage of C?C bonds and led to the formation of ketone groups in the polymer backbone. A minor route (5%) of the reaction proceeded with the cleavage of C?C bonds, yielding two smaller fragments containing aldehyde and vinyl end groups. The availability of the cleavage route could lead to a dramatic decrease in the molecular weight, which, depending on the carboxidation degree, could be 1–2 orders of magnitude less than that of the initial material. Thus, the carboxidation of more than 15% of the polybutadiene C?C bonds transformed it into a C?O‐functionalized liquid rubber with a narrow molecular weight distribution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2510–2520, 2006     

Synthesis of the Stable Ordered Conjugated Polymer Poly(dibromodiacetylene) from an Explosive Monomer

Dibromobutadiyne is an extremely unstable compound that explodes at room temperature, even under inert atmosphere. This instability has limited the studies of dibromobutadiyne almost entirely to spectroscopic characterization. Here we report an approach to control the reactivity of dibromobutadiyne, via topochemical reaction in cocrystals, leading to the ordered polymer poly(dibromodiacetylene), PBDA. At low temperatures (?15 to ?18 °C), dibromobutadiyne can form cocrystals with oxalamide host molecules containing either pyridyl or nitrile side groups, in which halogen bonds align the dibromobutadiyne monomers for topochemical polymerization. The cocrystals with the bis(nitrile) oxalamide host undergo complete ordered polymerization to PBDA, demonstrated by solid‐state MAS‐NMR, Raman, and optical absorption spectroscopy. Once formed, the polymer can be separated from the host; unlike the monomer, PBDA is stable at room temperature.     

Arsole‐Containing π‐Conjugated Polymer by the Post‐Element‐Transformation Technique

A synthetic method to obtain an arsole‐containing π‐conjugated polymer by the post‐transformation of the organotitanium polymer titanacyclopentadiene‐2,5‐diyl unit with an arsenic‐containing building block is described. The UV/Vis absorption maximum and onset of the polymer were observed at 517 nm and 612 nm, respectively. The polymer exhibits orange photoluminescence with an emission maximum (E_max) of 600 nm and the quantum yield (Φ) of 0.05. The polymer proved to exhibit a quasi‐reversible redox behavior in its cyclic voltammetric (CV) analysis. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated to be ?5.43 and ?3.24 eV, respectively, from the onsets for oxidation and reduction signals in the CV analysis. Further chemical modification of the arsole unit in the π‐conjugated polymer by complexation of gold(I) chloride occurred smoothly resulting in the bathochromic shift of the UV/Vis absorption and lowering of the LUMO energy level.     

Narrow band gap D–A copolymer of indacenodithiophene and diketopyrrolopyrrole with deep HOMO level: Synthesis and application in field‐effect transistors and polymer solar cells

A novel fused ladder alternating D–A copolymer, PIDT–DPP, with alkyl substituted indacenodithiophene (IDT) as donor unit and diketopyrrolopyrrole (DPP) as acceptor unit, was designed and synthesized by Pd‐catalyzed Stille‐coupling method. The copolymer showed good solubility and film‐forming ability combining with good thermal stability. PIDT–DPP exhibited a broad absorption band from 350 to 900 nm with an absorption peak centered at 735 nm. The optical band gap determined from the onset of absorption of the polymer film was 1.37 eV. The highest occupied molecular orbital level of the polymer is as deep as ?5.32 eV. The solution‐processed organic field‐effect transistor (OFETs) was fabricated with bottom gate/top contact geometry. The highest FET hole mobility of PIDT–DPP reached 0.065 cm² V^?1 s^?1 with an on/off ratio of 4.6 × 10⁵. This mobility is one of the highest values for narrow band gap conjugated polymers. The power conversion efficiency of the polymer solar cell based on the polymer as donor was 1.76% with a high open circuit voltage of 0.88 V. To the best of our knowledge, this is the first report on the photovoltaic properties of alkyl substituted IDT‐based polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Perylene diimide copolymers with dithienothiophene and dithienopyrrole: Use in n‐channel and ambipolar field‐effect transistors

Solution‐processable polymers consisting of perylene diimide (PDI) acceptor moieties alternating with dithienothiophene (DTT), N‐dodecyl‐dithienopyrrole (DTP), or oligomers of these donor groups have been synthesized. We have, in addition to varying the donor, varied the N,N′ substituents of the PDIs. The thermal, optical, electrochemical, and charge‐transport properties of the polymers have been investigated. The polymers show broad absorption extending from 300 to 1000 nm with optical band gaps as low as 1.2 eV; the band gap decreases with increasing the conjugation length of donor block, or by replacement of DTT by DTP. The electron affinities of the polymers, estimated from electrochemical data, range from ?3.87 to ?4.01 eV and are slightly affected by the specific choice of donor moiety, while the estimated ionization potentials (?5.31 to ?5.92 eV) are more sensitive to the choice of donor. Bottom‐gate top‐contact organic field‐effect transistors based on the polymers generally exhibit n‐channel behavior with electron mobilities as high as 1.7 × 10^–2 cm²/V/s and on/off ratios as high as 10⁶; one PDI‐DTP polymer is an ambipolar transport material with electron mobility of 4 × 10^–4 cm²/V/s and hole mobility of 4 × 10^–5 cm²/V/s in air. There is considerable variation in the charge transport properties of the polymers with the chemical structures. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of a novel polymer based on anthracene moiety for organic thin film transistor

We have designed and synthesized a new polymer, which could be used in the organic thin film transistor (OTFT). Poly[2,6‐bis(3′‐dodecythiophene‐2′‐yl)anthracene] (PDTAn), which is composed with anthracene moiety and dodecyl alkyl thiophene, was synthesized by oxidative polymerization using iron (III) chloride. The mole ratio of FeCl₃ and monomer (4.2:1), keeping low temperature during the initiation reaction, amount of solvent, and dropping order were very important for oxidative polymerization without crosslinking. The molecular weight of the polymer (M_w) was measured to be 40,000 with 2.85 of polydispersity index by GPC. The physical and optical properties of the polymer were characterized by differential scanning calorimetry (DSC), cyclic voltammetry (CV), and optical absorption and photoluminescence (PL) spectroscopy. A field‐effect mobility of 1.1 × 10^?4 cm² V^?1 S^?1, a current on/off ratio of 10⁵, and the V_th at ?15.2 V had been obtained for OTFTs using this polymer semiconductor by solution coating. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5115–5122, 2008     

Hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s: Synthesis,characterization, end‐group modification,and optical properties

Novel AB₂‐type monomers such as 3,5‐bis(4‐methylolphenoxy)benzoic acid ( monomer 1 ), methyl 3,5‐bis(4‐methylolphenoxy) benzoate ( monomer 2 ), and 3,5‐bis(4‐methylolphenoxy)benzoyl chloride ( monomer 3 ) were synthesized. Solution polymerization and melt self‐polycondensation of these monomers yielded hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s. The structure of these polymers was established using FTIR and ¹H NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 2.0 × 10³ to 1.49 × 10⁴ depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End‐group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4‐(decyloxy)benzoic acid and methyl red dye. The end‐capping groups were found to change the thermal properties of the polymers such as T_g. The optical properties of hyperbranched polymer and the dye‐capped hyperbranched polymer were investigated using ultraviolet‐absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414–5430, 2008     

Organosilicon polymers with alternating σ- and π-conjugated systems

A series of organosilicon polymers containing polysilane and diethynylaryl units along the polymer backbone were synthesized and examined with respect to their optical absorptions. The results indicate that delocalization takes place through the σ–π conjugated system. Lengthening of π-conjugation leads to lower excitation energies while nearly identical UV–vis spectra are observed with increased Si–Si chain length. Introducing a thiophene unit into the π-system instead of a benzene unit leads to a bathochromic shift reflecting greater σ–π delocalization. The polymers undergo photodegradation, probably via cleavage of the Si–Si bonds, and thermal crosslinking by reaction at the C≡C triple bonds. When doped with iodine, these polymers become semiconducting with conductivity of the order of 10^?4 S cm^?1.     

Routes to Hydrogen Bonding Chain‐End Functionalized Polymers

The contribution of supramolecular chemistry to polymer science opens new perspectives for the design of polymer materials exhibiting valuable properties and easier processability due to the dynamic nature of non‐covalent interactions. Hydrogen bonding polymers can be used as supramolecular units for yielding larger assemblies that possess attractive features, arising from the combination of polymer properties and the responsiveness of hydrogen bonds. The post‐polymerization modification of reactive end‐groups is the most common procedure for generating such polymers. Examples of polymerizations mediated by hydrogen bonding‐functionalized precursors have also recently been reported. This contribution reviews the current synthetic routes toward hydrogen bonding sticker chain‐end functionalized polymers.     

Oxidation and epoxidation of poly(1,3‐cyclohexadiene)

Poly(1,3‐cyclohexadiene) (PCHD) derivatives were synthesized via facile chemical modification reactions of the residual double bond in the repeat unit. The oxidation and degradation of PCHD was investigated to enable subsequent controlled epoxidation reactions. PCHD exhibited a 15% weight loss at 110 °C in the presence of oxygen. The oxidative degradation, demonstrated by gel permeation chromatography (GPC) and ¹H NMR spectroscopy, was attributed to main‐chain scission. Aldehyde and ether functional groups were introduced into the polymer during the oxidation process. PCHD was quantitatively epoxidized in the absence of deleterious oxidation with meta‐chloroperoxybenzoic acid. ¹H and ¹³C NMR spectroscopy confirmed that polymers with controlled degrees of epoxidation were reproducibly obtained. Epoxidized PCHD exhibited a glass‐transition temperature at 154 °C, which was slightly higher than that of a PCHD precursor of a nearly equivalent molecular weight. Moreover, GPC indicated the absence of undesirable crosslinking or degradation, and the molecular weight distributions remained narrow. The thermooxidative stability of the fully epoxidized polymer was compared to that of the PCHD precursor, and the epoxidized PCHD exhibited an initial weight loss at 250 °C in oxygen, which was 140 °C higher than the temperature for PCHD. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 84–93, 2003     

Chemoselective Phototransformation of CH Bonds on a Polymer Surface through a Photoinduced Cerium Recycling Redox Reaction

It is generally accepted that Ce⁴⁺ is unable to directly oxidize unreactive alkyl C?H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl₃/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce³⁺ was first photooxidized to form Ce⁴⁺ in the presence of H⁺, and the in situ formed Ce⁴⁺ then performs an oxidation reaction on the C?H bonds of the polymer surface to form surface‐carbon radicals for radical graft polymerization reactions and functional‐group transformations, while reducing to Ce³⁺ and releasing H⁺ in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C?H bonds on polymer surfaces into small‐molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer‐surface modification.     

Benzotriazole and benzodithiophene containing medium band gap polymer for bulk heterojunction polymer solar cell applications

An alternating donor‐acceptor copolymer based on a benzotriazole and benzodithiophene was synthesized and selenophene was incorporated as π‐bridge. The photovoltaic and optical properties of polymer were studied. The copolymer showed medium band gap and dual absorption peaks in UV‐Vis absorption spectra. Photovoltaic properties of P‐SBTBDT were performed by conventional device structure. The OSC device based on polymer: PC₇₁BM (1:1, w/w) exhibited the best PCE of 3.60% with a V_oc of 0.67 V, a J_sc of 8.95 mA/cm², and a FF of 60%. This finding was supported with morphological data and space charge limited current (SCLC) mobilities. The hole mobility of the copolymer was estimated through SCLC model. Although surface roughness of the active layer is really high, mobility of a polymer was found as 7.46 × 10^?3 cm²/Vs for optimized device that can be attributed to Se?Se interactions due to the larger, more‐polarizable Se atom. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 528–535     

Nanostructured polymetallaynes of controlled length: Synthesis and characterization of oligomers and polymers from 1,1′‐bis‐(ethynyl)4,4′‐biphenyl bridging Pt(II) or Pd(II) centers

The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu₃)₂ (C?C? C₆H₄? C₆H₄? C?C? )]_n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR ³¹P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007     

Modulation of electronic properties of π‐conjugated copolymers derived from naphtho[1,2‐b:5,6‐b′]dithiophene donor unit: A structure‐property relationship study

A set of three donor‐acceptor conjugated (D‐A) copolymers were designed and synthesized via Stille cross‐coupling reactions with the aim of modulating the optical and electronic properties of a newly emerged naphtho[1,2‐b:5,6‐b′]dithiophene donor unit for polymer solar cell (PSCs) applications. The PTNDTT‐BT , PTNDTT‐BTz , and PTNDTT‐DPP polymers incorporated naphtho[1,2‐b:5,6‐b′]dithiophene ( NDT ) as the donor and 2,2′‐bithiazole ( BTz ), benzo[1,2,5]thiadiazole ( BT ), and pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione ( DPP ), as the acceptor units. A number of experimental techniques such as differential scanning calorimetry, thermogravimetry, UV–vis absorption spectroscopy, cyclic voltammetry, X‐ray diffraction, and atomic force microscopy were used to determine the thermal, optical, electrochemical, and morphological properties of the copolymers. By introducing acceptors of varying electron withdrawing strengths, the optical band gaps of these copolymers were effectively tuned between 1.58 and 1.9 eV and their HOMO and LUMO energy levels were varied between ?5.14 to ?5.26 eV and ?3.13 to ?3.5 eV, respectively. The spin‐coated polymer thin film exhibited p‐channel field‐effect transistor properties with hole mobilities of 2.73 × 10^?3 to 7.9 × 10^?5 cm² V^?1 s^?1. Initial bulk‐heterojunction PSCs fabricated using the copolymers as electron donor materials and [6,6]‐phenyl C71 butyric acid methyl ester (PC₇₁BM) as the acceptor resulted in power conversion efficiencies in the range of 0.67–1.67%. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2948–2958     

Main-chain,syndioregic, high-glass transition temperature polymer for nonlinear optics: Synthesis and characterization

A new main-chain syndioregic (head-to-head) NLO polymer was synthesized. The glass transition temperature of high molecular weight polymer was found to be 208°C, and the polymer has minimal weight loss at temperatures to at least 250°C owing to the incorporation of hydrogen bonding moieties and rigid bridging groups. The polymer was further characterized using nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The study of the nonlinear optical properties of this polymer are in progress. © 1993 John Wiley & Sons, Inc.