Synthesis and properties of polythiophenes with conjugated side‐chains containing carbon–carbon double and triple bonds

Two soluble side‐chain conjugated polythiophenes, poly{3‐[2‐(4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3OPVT) and poly{3‐(4‐octyloxy‐phenylethynyl)‐thiophene} (P3OPET) have been synthesized successfully. In P3OPVT and P3OPET, substituted benzene rings are connected with the polythiophene backbone through trans carbon–carbon double bond and carbon–carbon triple bond, respectively. Absorption spectra of the P3OPVT and P3OPET both show two absorption peaks located in UV and visible region, respectively. The results of optical and electrochemical measurements indicate that the conjugated side‐chains can reduce the bandgap effectively. This type of side‐chain conjugated polythiophenes may be promising for the applications in polymer photovoltaic cells and field effect transistors. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2206–2214, 2006     

Synthesis and photovoltaic properties of conjugated side chains polymers with different electron‐withdrawing and donating end groups

A series of novel low band gap polymers containing conjugated side chains with 4,7‐dithien‐5‐yl‐2,1,3‐benzodiathiazole and different electron‐withdrawing end groups of aldehyde ( PT‐DTBTCHO ), 2‐ethylhexyl cyanoacetate ( PT‐DTBTCN ), 1,3‐diethyl‐2‐thiobarbituric acid ( PT‐DTBTDT ), and electron‐donating end group of 2‐methylthiophene ( PT‐DTBTMT ) have been designed and synthesized. All polymers exhibit good solubility in common organic solvents, film‐forming ability, and thermal stability. These conjugated polymers show the broad ultraviolet‐visible absorption and the narrow optical band gaps in the range of 1.65–1.90 eV. Through changing the end group of conjugated side chains, the photophysical properties and energy levels of the polymers were tuned effectively. Bulk heterojunction solar cells based on the blend of these polymers and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) reached the best power conversion efficiency (PCE) of 2.72%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Anthracene‐ and thiophene‐containing MEH‐PPE‐PPVs: Synthesis and study of the effect of the aromatic ring position on the photophysical and electrochemical properties

This contribution reports on the synthesis and characterization of thiophene‐ ( P1 , P2 , and P3 ) and anthracene‐ ( P4 and P5) containing PPE‐PPV copolymers. The thermostable, soluble and film‐forming polymers were fully characterized by NMR, IR and ELEM . ANAL .; they exhibit high molar masses with polydispersity indices below 2.5. The position of the thiophene in the polymeric backbone has insignificant influence on the spectroscopic properties of the polymers. In contrast, the anthracene‐containing polymers reveal position dependent optical properties. A constant bathochromic shift of 50 nm was observed going from P4 , where anthracene is surrounded by two double bonds, to P5 , where anthracene is at the bridge between a triple bond and a double bond, as well as from P5 to P6 where anthracene is surrounded by two triple bonds. This correlates to the decrease of the observed anthracene band around 255 nm going from P4 through P5 to P6 , amounting to the degree of contribution of the anthracene unit to the main chain conjugation. The phenomenon known as CN‐PPV effect was observed in the case of P4 [Φ_f (solution) = 3%, Φ_f (solid) = 13%]. Electrochemical studies carried out under absolute inert conditions revealed lower electrochemical band gap energies, E , than E . © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2243–2261, 2009     

Effect of side chain conjugation lengths on photovoltaic performance of two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with side chains

Two new two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with different π conjugation lengths as side chains, called PDPPMTD and PDPPBTD , were designed and synthesized for use in polymer solar cells (PSCs). The resulting copolymers in the thin film state displayed broad absorption in the visible range with an absorption edge at over 1000 nm, and both had relatively low‐lying HOMO levels, at ?5.20 and ?5.18 eV for PDPPMTD and PDPPBTD , respectively. The power conversion efficiency (PCE) of the PSC that was based on PDPPBTD /PC61BM (w/w = 1:2) reached 4.10 % with a Jsc of 14.5 mA/cm2, a Voc of 0.59 V and an FF of 48%, while PDPPMTD /PC61BM (w/w = 1:2) had a PCE of 2.96% with a Jsc of 12.6 mA/cm2, a Voc of 0.60 V, and an FF of 39%. These results indicate that subtle tuning of the chemical structure can significantly influence Jsc and FF. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2878–2889     

Novel two‐dimensional donor–acceptor conjugated polymers containing quinoxaline units: Synthesis,characterization, and photovoltaic properties

Novel two‐dimensional donor–acceptor (D–A) structured conjugated polymers, P1–P4, were designed and synthesized by introducing electron‐deficient quinoxaline as core and electron‐rich alkoxyl‐phenylenevinylene in side chains and p‐phenylenevinylene, triphenylamine, or thiophene in main chain. Benefited from the D–A structures, the polymers possess low bandgaps of 1.75 eV, 1.86 eV, 1.59 eV, and 1.58 eV for P1, P2, P3, and P4, respectively, and show broad absorption band in the visible region: the shorter wavelength absorption peak at ～400 nm ascribed to the conjugated side chains and the longer wavelength absorption peak between 500 nm and 750 nm belonging to the absorption of the conjugated main chains. Especially, the absorption band of P4 film covers the whole visible range from 300 nm to 784 nm. The power conversion efficiencies of the polymer solar cells based on P1–P4 as donor and PCBM as acceptor are 0.029%, 0.14%, 0.46%, and 0.57%, respectively, under the illumination of AM 1.5, 100 mW/cm². The polymers with the low bandgap and broad absorption band are promising photovoltaic materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4038–4049, 2008     

Effects of substituted side‐chain position on donor–acceptor conjugated copolymers

The optical properties and electrical properties of a series of low‐band‐gap conjugated copolymers, in which alkyl side chains were substituted at various positions, were investigated using donor–acceptor conjugated copolymers consisting of a cyclopentadithiophene derivative and dithienyl‐benzothiadiazole. With substituted side chains, the intrinsic properties of the copolymers were significantly altered by perturbations of the intramolecular charge transfer. The absorption of poly[2, 6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3,4‐b′]dithiophene)‐alt‐4, 7‐bis(4‐octyl‐thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐ttOTBTOT ( P2 )], which assumed a tail–tail configuration, tended to blue shift relative to the absorption of poly[2,6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3,4‐b′]dithiophene)‐alt‐4,7‐bis (thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐TBTT ( P1 )]. The absorption of poly[2,6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3, 4‐b′]dithiophene)‐alt‐4,7‐bis(3‐octyl‐thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐hhOTBTOT ( P3 )], which assumed a head–head configuration, was blue shifted relative to that of P2 . The electrical transport properties of field‐effect transistors were sensitive to the side chain position. The field‐effect mobility in P2 (μ₂ = 1.8 × 10^?3 cm²/V s) was slightly lower than that in P1 (μ₁ = 4.9 × 10^?3 cm²/V s). However, the mobility of P3 was very low (μ₃ = 3.8 × 10^?6 cm²/V s). Photoexcitation spectroscopy showed that the charge generation efficiency (shown in transient absorption spectra) and polaron pair mobility in P1 and P2 were higher than in P3 , yielding P1 and P2 device performances that were better than the performance of devices based on P3 . © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Low‐bandgap donor–acceptor copolymers with 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5]thiadiazole: synthesis,optical, electrochemical,and photovoltaic properties

Two new low‐bandgap alternating copolymers (CEHTF and CEHTP) consisting of 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5] thiadiazole and 9,9‐bis(2‐ethylhexyl)fluorene or 2,5‐bis(isopentyloxy)benzene were synthesized by Suzuki coupling reaction of corresponding comonomers. Their optical, electrochemical, and photovoltaic (PV) properties were studied and are reported. Both the copolymers exhibited long‐wavelength absorption covering the whole visible spectral region, which is in CEHTP thin films extended up to near infrared region, ambipolar redox properties, and electrochromism. High‐electron affinities and low‐optical bandgap values, 1.37 and 1.15 eV, were determined for CEHTF and CEHTP, respectively. PV devices with bulk heterojunction made of blends of copolymers and fullerene derivative [6,6]‐phenyl‐C⁶¹‐butyric acid methyl ester ([60]PCBM) were prepared and characterized. Effects of intramolecular charge transfer strength and side‐chain nature and length on photophysical properties are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Incorporation of a conjugated side‐chain in regioregular polythiophenes: Chiroptical properties and selective oxidation

The synthesis, aggregation, and optical properties of a chiral, regioregular polythiophene, substituted with a conjugated substituent, are described. The polymer was prepared using a Stille coupling reaction. The fact that the side‐chain contributes to the absorption (UV‐vis), emission (fluorescence), and redox behavior (cyclic voltammetry) of the material demonstrates that the substituent contributes to the electronic properties. It was shown that the conjugated side‐chain chirally stacks in conditions in which the polymer backbone aggregates, which demonstrates the ability of conjugated polymers to induce a (chiral) lamellar organization of conjugated moieties, present in their side‐chain. The aggregation of both the side‐chain and the backbone was monitored using UV‐vis and CD spectroscopy. Finally, it is shown that the conjugated side‐chain can selectively be oxidized, without oxidizing the polythiophene backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1891–1900, 2009     

High performance polymer field‐effect transistors based on polythiophene derivative with conjugated side chain

Poly(3‐[2‐(5‐hexyl‐2‐thienyl) ethenyl]‐2,2′‐bithiophene) ( P2 , see Scheme 1 ) with conjugated thienylvinyl side chain was synthesized by copolymerization of the thiophene units with and without conjugated side chain with Pd‐catalyzed Stille coupling method. For comparison, P1 with the hexyl side chain instead of conjugated side chain was also synthesized. P2 film shows broad absorption in the visible region with absorption edge at about 700 nm. The solution‐processed polymer field‐effect transistors were fabricated and characterized with bottom gate/top contact geometry. The organic field‐effect transistors (OFET) based on P2 showed an average hole mobility of about 0.034 cm²/Vs (the highest value reached 0.061 cm²/Vs) upon annealing at about 180 °C for 30 min, with a threshold voltage of ?1.15 V and an on/off ratio of 10⁴ with n‐octadecyltrichlorosilane (OTS) modified SiO₂ substrate. In comparison, the OFET based on P1 displayed a hole mobility of 8.9 × 10^–4 cm²/Vs and an on/off ratio of 10⁴ with OTS modified SiO₂ substrate. The results indicate that the polythiophene derivative with conjugated thienylvinyl side chain is a promising polymer for the application in polymer field‐effect transistors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5304–5312, 2009     

Ethynylene‐containing donor–acceptor alternating conjugated polymers: Synthesis and photovoltaic properties

Four ethynylene‐containing donor‐acceptor alternating conjugated polymers P1 – P4 with 2,5‐bis(dodecyloxy) substituted phenylene or carbazole as the donor unit and benzothiadiazole (BTZ) as the acceptor unit were synthesized and used as donor polymers in bulk heterojunction polymer solar cells. The optical, electrochemical, and photovoltaic properties of these four polymers with the ethylene unit located at different positions of the polymer chains were systematically investigated. Our results demonstrated that absorption spectra and the HOMO and LUMO energy levels of polymers could be tuned by varying the position of the ethynylene unit in the polymer chains. Photovoltaic devices based on polymer/PC₇₁BM blend films spin coated from chloroform and dichlorobenzene solutions were investigated. For all four polymers, open circuit voltages (V_oc) higher than 0.8 V were obtained. P4 , with ethynylene unit between BTZ and thiophene, shows the best performance among these four polymers, with a V_oc of 0.94 V, a J_sc of 4.2 mA/cm², an FF of 0.40, and a PCE of 1.6%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and photovoltaic properties of novel (X-DADAD)n conjugated polymers with fluorene and phenylene blocks

Novel fluorene- and phenylene-based conjugated polymers with the TBTBT molecular framework consisting of the thiophene (T) and benzothiadiazole (B) building blocks have been synthesized and investigated. It has been demonstrated that the variation of X building blocks with branched side chains in (X-TBTBT)_n-type structures, as well as the introduction of fluorine into the main chain, strongly affects the optical, electronic and physicochemical properties of the obtained polymers. The phenylene-based polymer with a fluorine- loaded TBTBT block achieves a power conversion efficiency of 7% in organic solar cells, which can be further improved by optimizing the active layer morphology.     

Synthesis and characterization of soluble low‐bandgap oligothiophene‐[all]‐S,S‐dioxides‐based conjugated oligomers and polymers

The synthesis and characterization of a new family of soluble oligothiophene‐S,S‐dioxides and their use as building blocks to form polythiophene‐S,S‐dioxides via microwave‐assisted Stille coupling polymerization are described. Incorporation of the sulfone group into the polythiophene backbone leads to narrowing of the polymer bandgap, and while the energies of both Frontier orbitals in polythiophene‐S,S‐dioxide are lower with respect to polythiophenes, this tendency is considerably stronger for the lowest unoccupied molecular orbital than for the highest occupied molecular orbital, resulting in greater electron‐accepting ability. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of through‐space conjugated polymers based on π–π stacked 1,3‐biarylpropane tethering units

Novel skipped‐π polymers in which the π‐components are connected with 2‐substituted trimethylene tethering units exhibit bathochromically shifted, broadened ultraviolet absorption with a unique lower‐energy absorption band and a largely red‐shifted fluorescent emission. These results suggest that through‐space π–π interactions owing to a stair‐like stacking substructure in these polymers extend the π‐conjugation of the components in the ground and excited states. As the photophysical properties of the polymers observed both in a solution and in a dried film are similar to those of the J‐aggregates of π‐molecules, these polymers may be considered as pseudo J‐stacking (or J‐like‐stacking) polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3412–3419     

Synthesis and characterization of soluble conjugated polymers having pyrene moiety in the main chain

Three new alternating conjugated polymers consisting of pyrene and 3‐dodecylthiophene ( PPyMT ), 4,4′‐didodecyl‐2,2′‐bithiophene ( PPyBT ), or 9,9‐didodecylfluorene ( PPyFlu ) moieties have been prepared using Suzuki coupling reaction or Sugimoto approaches. The polymers were readily soluble in common organic solvents and exhibited good thermal stability in nitrogen and air atmospheres. The structures and optical properties of the polymers were characterized by NMR, FTIR, XRD, UV–vis, and fluorescence spectroscopy. PPyMT and PPYBT showed blue‐light emission in solution, whereas PPyFlu performed blue‐light emitting in film state. The polymers exhibited an intermolecular aggregation and structural ordering due to pyrene–pyrene π–π stacking interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Optical properties of chiral nematic side‐chain copolymers bearing cholesteryl and azobenzene building blocks

Thermotropic chiral nematic (N*) side‐chain copolymers (CPs) bearing cholesteryl and azobenzene units were synthesized to investigate the structure–property relationships of the acrylates of the chiral, achiral, and photochromic monomers of free radical polymerization‐derived polymers. The polar effect of chlorine substitution on the benzene ring of the chiral monomer (M3*) widened the mesophase transition temperature only at the monomer level, but no remarkable effect on the mesomorphic, optical or thermochromism of the corresponding CPs was observed. An examination of the CPs prepared using differential scanning calorimetry and hot‐stage polarizing microscopy showed that all the CPs exhibited a cholesteric nematic phase (N*), and increasing the content of the cholesteryl units in the CPs displayed only the N* phase over a much wider temperature range. On cooling from the isotropic melt of N* CPs, selective reflections of visible light that changed from short to long wavelengths were observed. The photolysis of CPs revealed that CP1 – CP4 undergo reversible photoisomerization and that CP5 and CP6 undergo irreversible photoisomerization. The rate of isomerization depends on the type (? N?N? , ? CH?CH? , and both) and content of photochromic units in the CPs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

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     

Synthesis of imidazole‐containing conjugated polymers bearing phenol unit as side group and excited state intramolecular proton transfer‐mediated fluorescence

Dibromobenzimidazole and dibromoimidazole bearing hydroxyl group‐protected phenol unit ( 1 and 2 ) were prepared and they showed an intramolecular hydrogen bonding between ether oxygen and amino proton of imidazole. The palladium‐catalyzed Suzuki coupling polymerization of 1 and 2 with benzene bis(boronic acid) derivatives gave soluble polymers ( 3 and 4 ), where the molecular weights were limited probably due to the coordination ability of imidazole to palladium metal. The phenol hydroxyl groups were subsequently deprotected using BBr₃ to obtain 3 ′ and 4 ′. From the ¹H NMR spectra, the complete conversion to the hydroxyl group and the formation of another type of intramolecular hydrogen bonding between hydroxyl proton and imine nitrogen were confirmed. In the UV and PL spectra of 3 ′ and 4 ′, the excited state intramolecular proton transfer (ESIPT) occurred to shift the emission spectra toward lower energy region compared to 3 and 4 . Especially, the PL spectrum of 3 ′ demonstrated large stokes shift (145 nm) in THF solution. The ESIPT‐mediated fluorescence was influenced by the addition of methanol and trifluoroacetic acid, which inhibited the formation of intramolecular hydrogen bonding. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4822–4829, 2009     

Synthesis,hole mobility,and photovoltaic properties of two alternating poly[3‐(hex‐1‐enyl)thiophene‐co‐thiophene]s

Two alternating poly[3‐(hex‐1‐enyl)thiophene‐co‐thiophene]s, Pa (with 77% trans‐isomer and 23% cis‐isomer) and Pb (with 100% trans‐isomer), were synthesized by the coupling of 2,5‐dibromo‐3‐hex‐1‐enyl‐thiophene to 2,5‐bis(tributylstannyl)thiophene via a Stille reaction and compared with poly(3‐hexylthiophene‐co‐thiophene) ( P1 ) to study the effect of changing the carbon(α)–carbon(β) single bond into a carbon–carbon double bond on the properties of the polymers. From P1 to Pb and to Pa , the ultraviolet–visible absorption peaks of the polymers were slightly redshifted, and their electrochemical bandgaps decreased by 0.05–0.1 eV. X‐ray diffraction analysis indicated that Pa had a better lamellar structure than Pb . The hole mobilities of the three polymers, determined with the space‐charge‐limited current model, were 5.23 × 10^?6 ( P1 ), 2.34 × 10^?4 ( Pb ), and 7.02 × 10^?4 cm²/V s ( Pa ). The power conversion efficiencies (PCEs) of polymer solar cells based on the three polymers were 0.87 ( P1 ), 1.16 ( Pb ), and 1.70% ( Pa ). The increase in the hole mobility and PCE revealed the important effect of changing the carbon(α)–carbon(β) single bond into a carbon–carbon double bond on the properties of polythiophene derivatives containing 3‐alkylthiophene. The strategy used in this work enlarges the thinking to obtain novel, efficient donor polymers for optoelectronic applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 629–638, 2007     

Synthesis and photovoltaic properties of two‐dimensional copolymers based on novel benzothiadiazole and quinoxaline acceptors with conjugated dithienylbenzothiadiazole pendants

Two novel acceptors of benzo[c][1,2,5]thiadiazole and quinoxaline with conjugated dithienylbenzothiadiazole pendants were first designed and synthesized for building efficient photovoltaic copolymers. Based on benzo[1,2‐b;3,4‐b′]dithiophene donors and the two acceptors, two new copolymers have been prepared by Stille coupling polymerization. The resulting copolymers were characterized by ¹H NMR, gel permeation chromatography, and thermogravimetric analysis. UV–Visible absorption and cyclic voltammetry measurements indicated that the two copolymers possessed strong and broad absorption in the range of 300–700 nm, and deep‐lying energy levels of highest occupied molecular orbitals. The polymer photovoltaic devices based on benzo[c][1,2,5]thiadiazole‐based copolymer/phenyl‐C₇₁‐butyric acid methyl ester exhibited a power conversion efficiency of 2.42%, attributed to its relatively better light‐harvesting ability and active film morphology. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 668–677     

Enhancing the electrochromic characteristics of conjugated polymer with TiO2 nano‐rods

Organic soluble, oleic acid capped TiO₂ nano‐rod was well‐mixed with the electrochromic polymer: Poly‐(4,4‐dioctylcyclopenta[2,1‐b:3,4‐b′]‐dithiophene (PDOCPDT) to form TiO₂/PDOCPDT nanocompsoite. TiO₂/PDOCPDT film showed high electrochemical stability and its coloration efficiency is 1.5 times of that for pure PDOCPDT. The function of TiO₂ nano‐rods can be regarded as a dispersion agent. PDOCPDT chains in TiO₂/PDOCPDT may have a less aggregated structure and more open morphology, therefore has higher coloration efficiency. TiO₂ may also act as electron transport or temporary electron storage centers, electrons can be transferred reversibly between PDOCPDT and TiO₂ nano‐rods. TiO₂/PDOCPDT is well‐soluble in CHCl₃, large area thin films can be fabricated reproducibly simply by spin coating. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1121–1130, 2008