Renewable resource‐based poly (m‐phenylenevinylene)s and their statistical copolymers: Synthesis,characterization, and probing of molecular aggregation and Forster energy transfer processes

We report a novel poly (m‐phenylenevinylene)s and their copolymers based on renewable resource starting material 3‐pentadecylphenol to trace the Forster energy transfer process and molecular aggregation in the π‐conjugated polymers. The new bisylide monomer was polymerized with bisaldehyde (or benzaldehyde) under Wittig‐Horner reaction conditions to prepare poly [(4‐methoxy‐6‐pentadecyl‐1, 3‐phenylenevinylene)‐alt‐(1, 3‐phenylenevinylene)] (m‐PPV) and its para‐counterpart poly [(4‐methoxy‐6‐pentadecyl‐1, 3‐phenylenevinylene)‐alt‐(1, 4‐phenylenevinylene)] (p‐PPV) and oligo‐phenylenevinylene model compound 4‐methoxy‐6‐pentadecyl‐1, 3‐distyrylbenzene (OPV). A series of with m‐ or p‐conjugated segments were also prepared by varying the m‐ and p‐content from 0 to 100% in the feed. The selective excitation of m‐conjugated segments in the copolymer by 310 nm light showed emission properties of pure p‐conjugated segments indicating the efficient Forster energy transfer process in segmented copolymers. Both solution quantum yields and the emission intensities increase up to 75% of para‐content in the copolymers. In the solid state, the increase in the p‐incorporation in the copolymer decreases the photoluminescent intensity almost by four times as compared to that of pure meta‐substituted PPV. The excitation spectra of the polymers confirmed a new peak at 400 nm corresponding to the aggregated polymer chains in the film, which is absent in the solution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3241–3256, 2008     

Dimensional Control of Block Copolymer Nanofibers with a π‐Conjugated Core: Crystallization‐Driven Solution Self‐Assembly of Amphiphilic Poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine)

With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT₂₃‐b‐P2VP₁₁₅ (block ratio=1:5) and P3HT₄₄‐b‐P2VP₁₁₅ (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH<iPrOH<nBuOH). Very long (>3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain‐extended P3HT blocks. The crystallinity and π‐conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide‐angle X‐ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT₂₃‐b‐P2VP₁₁₅ resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT₂₃‐b‐P2VP₁₁₅ unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (L_w/L_n <1.11) and lengths from about 100‐300 nm, that were dependent on the unimer‐to‐seed micelle ratio.     

Synthesis and self‐assembly in water of coil‐rod‐coil amphiphilic block copolymers with central π‐conjugated sequence

The purpose of this study is to correlate the nano‐organization in water of coil‐rod‐coil amphiphilic block copolymers constituted of a conjugated segment to their optoelectronic properties. The ABA block copolymer structures, easily achieved via coupling reactions, are based on conjugated rod of dihexylfluorene and 3,4‐ethylenedioxythiophene units linked to two flexible poly(ethylene oxide) or poly[(ethylene oxide)‐ran‐(propylene oxide)] chains. These well‐defined copolymers exhibited a range of specific morphologies in water, a good solvent of coil blocks and a bad solvent of the conjugated rod. Particularly, vesicles and micelles with spherical, cylindrical, or elongated shape were noticed. Correlations were attempted to be established between the weight percent of the conjugated sequence contained in the copolymers, the morphology of the nanostructures obtained by self‐assembly in solution and the resulting optical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4602–4616, 2008     

Near‐infrared electroluminescence from fluorene‐based copolymers

A series of random low band‐gap conjugated copolymers (PFO‐DDTQ) derived from 9,9‐dioctylfluorene (DOF) and 6,7‐dimethyl‐4,9‐di(4‐hexylthien‐2‐yl)‐[1,2,5]thiadiazolo[3,4‐g]quinoxalines (DDTQ) are prepared by the palladium‐catalyzed Suzuki coupling reaction. The obtained polymers are readily soluble in common organic solvents. The thin solid films of the polymers absorb light from 300 to 840 nm with two absorbance peaks at around 380 and 710 nm. Electroluminescent peaks are between 0.8 and 0.9 μm based on the polymers. The maximal external quantum efficiency reaches 0.30% with the emission peak at 824 nm from PFO‐DDTQ1 based devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3007–3013, 2008     

Linear π‐conjugated polymers containing 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit: Synthesis and optical properties

Some linear π‐conjugated polymers containing 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit were synthesized via Sonogashira or Suzuki reaction for the first time and characterized by IR, NMR, and GPC. Because of the introduction of 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit into π‐conjugated system, all polymers exhibited good thermal stability with high decomposition temperature. Their optical and electrochemical properties were investigated. Based on the 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit linked with different aromatic rings, the polymers showed the tunable fluorescence from blue to blue‐green emission with satisfied quantum yield. Cyclic voltammetry measurement indicated that the LUMO and HOMO levels of the polymers could be adjustable through the main‐chain structural modification. All polymers had low LUMO level (?2.86 to ?3.06 eV) due to the high‐electron affinity of triazine unit. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 702–712, 2008     

Herringbone and Helical Self‐Assembly of π‐Conjugated Molecules in the Solid State through CH/π Hydrogen Bonds

Self‐organization of organic molecules through weak noncovalent forces such as CH/π interactions and creation of large hierarchical supramolecular structures in the solid state are at the very early stage of research. The present study reports direct evidence for CH/π interaction driven hierarchical self‐assembly in π‐conjugated molecules based on custom‐designed oligophenylenevinylenes (OPVs) whose structures differ only in the number of carbon atoms in the tails. Single‐crystal X‐ray structures were resolved for these OPV synthons and the existence of long‐range multiple‐arm CH/π interactions was revealed in the crystal lattices. Alignment of these π‐conjugated OPVs in the solid state was found to be crucial in producing either right‐handed herringbone packing in the crystal or left‐handed helices in the liquid‐crystalline mesophase. Pitch‐ and roll‐angle displacements of OPV chromophores were determined to trace the effect of the molecular inclination on the ordering of hierarchical structures. Furthermore, circular dichroism studies on the OPVs were carried out in the aligned helical structures to prove the existence of molecular self‐assembly. Thus, the present strategy opens up new approaches in supramolecular chemistry based on weak CH/π hydrogen bonding, more specifically in π‐conjugated materials.     

Solvent Control over Supramolecular Gel Formation and Fluorescence for a Highly Crystalline π‐Conjugated Polymer

In π‐conjugated polymers (πCPs), crystallinity and fluorescence typically exhibit a trade‐off relationship. Here, we have synthesized a highly crystalline and fluorescent π‐conjugated polymer with a simple alternating structure of 1,2,4,5‐tetrafluorophenylene and 3,3′‐dihexyl‐2,2′‐bithiophene units. In film, the polymer exhibited efficient red‐colored fluorescence, an improved quantum yield (Φ_sol=13 %→Φ_film=23 %) and a crystalline structure. Interestingly, supramolecular gel formation occurred in appropriate solvents, and the macrostructure and fluorescence properties of the gel could be directly controlled by the choice of the solvent. The polymer self‐assembled into a spherical form that exhibited red fluorescence in non‐aromatic solvent (1,2‐dichloroethane) and into a fibrous form that exhibited yellow fluorescence in aromatic solvent (mesitylene).     

An X‐shaped π‐conjugated polymer comprising of fluorene units and anthracene units with high efficiency. Synthesis and optical and electrochemical properties

A new X‐shaped π‐conjugated monomer comprising of fluorene units and anthracene units was synthesized, and it was used to fabricate the new X‐shaped π‐conjugated polymers and investigate the properties of the new polymers. Using different molar ratios between such monomer and a fluorene monomer gave three polymers that showed higher absolute PL quantum yields than the linear polyfluorene (PF) in the solid state. After thermal annealing at 200 °C for 4 h, the linear PF showed an additional bathochromic emission at about 550 nm, whereas such red‐shifted emission was fully eliminated for the X‐shaped polymers. The electroluminescent devices based on the X‐shaped polymers with a configuration of ITO/PEDOT:PSS/polymer/LiF/Ca/Al displayed blue emission with low turn‐on voltage and high brightness. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5616–5625, 2008     

A Typical Metal‐Ion‐Responsive Color‐Tunable Emitting Insulated π‐Conjugated Polymer Film

We report the synthesis of an insulated π‐conjugated polymer containing 2,2′‐bipyridine moieties as metal coordination sites. Metal coordination to the polymer enabled easy and reversible tuning of the luminescent color without changes to the main chain skeleton. The permethylated α‐cyclodextrin (PM α‐CD)‐based insulation structure allowed the metalated polymers to demonstrate efficient emission even in the solid state, with identical spectral shapes to the dilute solutions. In addition, the coordination ability of the metal‐free polymer was maintained in the solid state, resulting in reversible changes in the luminescent color in response to the metal ions. The synthesized polymer is expected to be suitable for application in recyclable luminescent sensors to distinguish different metal ions.     

Synthesis and self‐organization properties of copolyurethanes based on perylenediimide and naphthalenediimide units

A series of perylene and naphthalene diimide‐containing random copolyurethanes with different ratios of perylene/naphthalene diimide content was synthesized and characterized. Copolymerization improved the solubility of these rigid aromatic diimides, and the copolymers were soluble in common organic solvents like chloroform, tetrahydrofuran, and so forth. The absorption spectra of perylene‐based copolymers showed a red‐shifted peak at a wavelength of 557 nm corresponding to J‐type aggregates. For naphthalene copolymers, the quenching of fluorescence at higher naphthalene incorporation suggested the presence of aggregates because of the extensive π‐π stacking of the aromatic core. FTIR spectroscopic analysis showed that the hydrogen bonding tendency of the polymer decreased with increase in perylene/naphthalene incorporation. The fluorescence spectra of the perylene polymers were exactly a mirror image of the absorption spectra. The fluorescence spectra of the naphthalene polymers at higher naphthalene incorporation showed a red‐shifted excimer like emission peak, which was assigned as static excimers based on their excitation spectra. These polymers could exhibit two types of secondary interaction modes, namely, hydrogen bonding (via urethane linkage) and π‐stacking (via aromatic perylene or naphthalene units) thus highlighting the importance of polymer design in inducing self‐organization at both low and high incorporation of the rigid bisimide moieties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1224–1235, 2009     

Benzodifuran‐containing well‐defined π‐conjugated polymers for photovoltaic cells

Two well‐defined alternating π‐conjugated polymers containing a soluble electroactive benzo[1,2‐b:4,5‐b′]difuran (BDF) chromophore, poly(BDF‐(9‐phenylcarbazole)) (PBDFC), and poly(BDF‐benzothiadiazole) (PBDFBTD) were synthesized via Sonogashira copolymerizations. Their optical, electrochemical, and field‐effect charge transport properties were characterized and compared with those of the corresponding homopolymer PBDF and random copolymers of the same overall composition. All these polymers cover broad optical absorption ranges from 250 to 750 nm with narrow optical band gaps of 1.78–2.35 eV. Both PBDF and PBDFBTD show ambipolar redox properties with HOMO levels of ?5.38 and ?5.09 eV, respectively. The field‐effect mobility of holes varies from 2.9 × 10^?8 cm² V^?1 s^?1 in PBDF to 1.0 × 10^?5 cm² V^?1 s^?1 in PBDFBTD. Bulk heterojunction solar cell devices were fabricated using the polymers as the electron donor and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester as the electron acceptor, leading to power conversion efficiencies of 0.24–0.57% under air mass 1.5 illumination (100 mW cm^?2). These results indicate that their band gaps, molecular electronic energy levels, charge mobilities, and molecular weights are readily tuned by copolymerizing the BDF core with different π‐conjugated units. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Oligo(p‐phenyleneethynylene)‐based coil–rod–coil triblock copolymer: Synthesis and controlled self‐organization in solution

The self‐assembling ability of block copolymers offers an attractive strategy for the organization of π‐conjugated polymers. This article reports the synthesis of a coil–rod–coil triblock copolymer consisting of oligo(p‐phenyleneethynylene) as the rodlike segment and polystyrene as the coil‐like segment. The chemical structure of the afforded triblock copolymer has been fully characterized by various spectroscopic techniques such as NMR, Raman, gel permeation chromatography, differential scanning calorimetry, ultraviolet–visible, and fluorescence spectroscopy. The small‐angle neutron scattering and photophysical measurements indicate that this triblock copolymer exhibits unique solvatochromatic behaviors through the interplay of aggregation‐induced π–π stacking and planarization of the conjugated backbone. Supramolecular gel nanostructures have been produced via the controlled assembly of the polymer into H‐aggregates. It has been demonstrated that the use of the solvent composition to influence chain conformations and thus to manipulate the packing of the conjugated polymer blocks is important for achieving control in the assembly of conducting polymers and associated optical characteristics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6007–6019, 2005     

Persistent and emission color tunable poly(phenylene‐ethynylene)s covered with polyhedral oligomeric silsesquioxanes

The development of chemically and thermally persistent blue‐, and green‐luminescent hybrid π‐conjugated polymers consisting of poly(phenylene‐ethynylene) conjugated backbone wrapped with the rigid three‐dimensional polyhedral oligomeric silsesquioxane (POSS) units was successfully achieved by means of the Sonogashira‐Hagihara coupling reaction. Because of the steric effect of POSS units, the luminescence stability of the conjugated backbone was significantly enhanced. Moreover, emission color was also easily tunable only by changing the ratio of POSS moieties incorporated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8112–8116, 2008     

Synthesis and characterization of novel π‐conjugated polymers with phosphole ring derivatives

Novel π‐conjugated polymers ( 8 – 10 ) were prepared by the palladium‐catalyzed Sonogashira coupling reaction of three kinds of phosphole‐ring‐containing monomers with 2,5‐dihexyloxyl‐1,4‐diethynylbenzene. The obtained polymers ( 8 – 10 ) were regioregulated with the 2,5‐substituted phosphole ring in the polymer main chain and characterized with ¹H, ¹³C, and ³¹P NMR and FTIR. Polymers 8 – 10 were found to have an extended π‐conjugated system according to the results of UV–vis absorption spectra. In the fluorescence emission spectra of 8 – 10 , moderate emission peaks were observed in the visible blue‐to‐green region. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2867–2875, 2007     

Synthesis,micellar structures,and multifunctional sensory properties of poly(3‐hexylthiophene)‐block‐poly(2‐(dimethylamino)ethyl methacrylate) rod‐coil diblock copolymers

We report the synthesis, micellar structures, and multifunctional sensory properties of new conjugated rod‐coil block copolymers, poly(3‐hexylthiophene)‐block‐poly(2‐(di methylamino)ethylmethacrylate)(P3HT‐b‐PDMAEMA). The new copolymers, synthesized by atom transfer radical polymerization of P3HT macroinitiator, consisted PDMAEMA coil lengths of 43, 65, and 124 repeating units. All the P3HT‐b‐PDMAEMA copolymers exhibit a similar low critical solution temperature in water around 33 °C. The micellar structures of the synthesized polymers were characterized by AFM, TEM, and dynamic light scattering, by varying temperature, pH, and water/THF composition. The micelles of P3HT₂₀‐b‐PDMAEMA₄₃ in water had a reversible size change from 75 ± 5 nm to 132 ± 5 nm on heating from 25 to 55 °C and reduced to the original size during cooling. In addition, the micellar size also showed a significant pH dependence, changing from 67 ± 8 nm (pH = 12) to 222 ± 6 nm (pH = 4), depending on the protonation of the PDMAEMA blocks and their electrostatic repulsion. The micellar structure of three P3HT‐b‐PDMAEMA copolymers changed from spheres, to vesicles, and finally to larger sphere micelles as the solvent composition varied from 0 to 100 wt % water in the mixed solvent. The different micellar structures of P3HT₂₀‐b‐PDMAEMA₄₃ solution led to a red‐shift on the absorption or photoluminescence spectra and exhibited the emission colors of yellow, orange, red, and dark red with increasing the water content. This study suggested that new copolymers had potential applications as multifunctional sensory materials toward temperature, pH, and solvent. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

π‐Conjugated Microporous Polymer Films: Designed Synthesis,Conducting Properties,and Photoenergy Conversions

Conjugated microporous polymers are a unique class of polymers that combine extended π‐conjugation with inherent porosity. However, these polymers are synthesized through solution‐phase reactions to yield insoluble and unprocessable solids, which preclude not only the evaluation of their conducting properties but also the fabrication of thin films for device implementation. Here, we report a strategy for the synthesis of thin films of π‐conjugated microporous polymers by designing thiophene‐based electropolymerization at the solution–electrode interface. High‐quality films are prepared on a large area of various electrodes, the film thickness is controllable, and the films are used for device fabrication. These films are outstanding hole conductors and, upon incorporation of fullerenes into the pores, function as highly efficient photoactive layers for energy conversions. Our film strategy may boost the applications in photocatalysis, energy storage, and optoelectronics.     

Synthesis of D‐π‐A‐π type benzodithiophene‐quinoxaline copolymers by direct arylation and their application in organic solar cells

Conjugated copolymers based on benzodithiophene (BDT) derivatives and thiophene‐quinoxaline‐thiophene (TQT) segments represent an efficient class of light harvesting materials for organic photovoltaic (OPV) applications. Commonly, BDT‐TQT copolymers are synthesized by Stille cross‐coupling polymerization. In this study, alkoxy and thienyl functionalized alternating BDT‐alt‐TQT copolymers are synthesized by direct arylation polymerization (DArP), using Ozawa conditions. An extensive optimization of the reaction conditions such as the catalytic system, solvent, temperature, base, and the concentration of the catalyst is accomplished. The optical and electrochemical properties of the copolymers obtained by DArP are compared to the reference polymers synthesized by Stille cross‐coupling polymerization. Finally, the optimized BDT‐alt‐TQT copolymers are incorporated into organic solar cells as electron donors. The solar cells of the DArP copolymers exhibit power conversion efficiencies up to 80% (rel.) of their Stille cross coupling analogues. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1457–1467     

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.

     

Redox‐Active Peptide‐Functionalized Quinquethiophene‐Based Electrochromic π‐Gel

An electrochromic system based on a self‐assembled dipeptide‐appended redox‐active quinquethiophene π‐gel is reported. The designed peptide‐quinquethiophene consists of a symmetric bolaamphiphile that has two segments: a redox‐active π‐conjugated quinquethiophene core for electrochromism, and peptide motif for the involvement of molecular self‐assembly. Investigations reveal that self‐assembly and electrochromic properties of the π‐gel are strongly dependent on the relative orientation of peptidic and quinquethiophene scaffolds in the self‐assembly system. The colors of the π‐gel film are very stable with fast and controlled switching speed at room temperature.     

Direct arylation polymerization toward ultra‐low bandgap poly(thienoisoindigo‐alt‐diketopyrrolepyrrole) conjugated polymers: The effect of β‐protection on the polymerization and properties of the polymers

Direct arylation polymerization between derivatives of dibromodiketopyrrolopyrrole (DPP) and thienoisoindigo (TIIG) resulted in two π‐conjugated copolymers with average molecular weights up to 24.0 kDa and bandgaps as low as 0.8 eV. The structural analysis of the obtained two polymers revealed well‐defined alternating conjugation backbones without obvious structural defects. The introduction of hexyl‐group in the β‐position of thiophene rings in the DPP units not only reduces the bandgap of conjugated polymer compared to a similar polymer containing bare‐thiophene flanked DPP but also affects polymer morphology in thin films. P‐type charge‐transport characteristics were observed for two polymers in organic field‐effect transistors with comparable hole mobilities. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3205–3213