Control of vertical distribution of thiophene‐based copolymers containing 4,7‐Dithien‐2‐yl‐benzo[C][1,2,5]thiadiazole and 3,6‐Dithien‐2‐yl‐pyrrolo[3,4‐C]pyrrole‐1,4(2H,5H)‐dione as Side Groups for Photovoltaics

Four new D—A type copolymers with 2D‐conjugated side‐chain identified PfToBT, PbToBT, PfTDPP and PbTDPP, containing two acceptors 4,7‐dithien‐2‐yl‐benzo[c][1,2,5]thiadiazole (DTBT), and diketopyrrolopyrrole (DPP) linked by thiophene donors, are obtained using Pd‐catalyzed Stille‐coupling reaction. These polymers show a broad visible‐near‐infrared absorption band (E_g = 1.79–1.66 eV) and possess a relatively low‐lying HOMO level at ?5.34 to ?5.12 eV. All the polymer:PC₇₀BM blend films showed edge‐on structure and have similar d_π‐spacing values. According to the structure of conjugated side‐chain, the vertical distributions of polymer chains and PC₇₀BM within the BHJ (bulk heterojunction) were different. When DPP used as an acceptor, conjugated side chains of the polymer coexisted with PC₇₀BM in same position. The BHJ film prepared from PfToBT, PbToBT had a discontinuous network between polymer and PC₇₀BM, whereas films from PfTDPP and PbTDPP formed continuous and evenly distributed network between them. This optimized vertical morphology promotes hole transport along respective pathways of polymers and fullerenes in the vertical direction, leading to high J_SC. PbTDPP shows PCE up to 2.9% (Jsc of 9.4 mA/cm², Voc of 0.68 V, and FF of 0.44). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2746–2759     

Donor–acceptor photovoltaic polymers based on 1,4‐dithienyl‐2,5‐dialkoxybenzene with intramolecular noncovalent interactions

Donor–acceptor (D–A) conjugated polymers bearing non‐covalent configurationally locked backbones have a high potential to be good photovoltaic materials. Since 1,4‐dithienyl‐2,5‐dialkoxybenzene ( TBT ) is a typical moiety possessing intramolecular S…O interactions and thus a restricted planar configuration, it was used in this work as an electron‐donating unit to combine with the following electron‐accepting units: 3‐fluorothieno[3,4‐b]thiophene ( TFT ), thieno‐[3,4‐c]pyrrole‐4,6‐dione ( TPD ), and diketopyrrolopyrrole ( DPP ) for the construction of such D–A conjugated polymers. Therefore, the so‐designed three polymers, PTBTTFT , PTBTTPD , and PTBTDPP , were synthesized and investigated on their basic optoelectronic properties in detail. Moreover, using [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as acceptor material, polymer solar cells (PSCs) were fabricated for studying photovoltaic performances of these polymers. It was found that the optimized PTBTTPD cell gave the best performance with a power conversion efficiency (PCE) of 4.49%, while that of PTBTTFT displayed the poorest one (PCE = 1.96%). The good photovoltaic behaviors of PTBTTPD come from its lowest‐lying energy level of the highest occupied molecular orbital (HOMO) among the three polymers, and good hole mobility and favorable morphology for its PC₇₁BM‐blended film. Although PTBTDPP displayed the widest absorption spectrum, the largest hole mobility, and regular chain packing structure when blended with PC₇₁BM, its unmatched HOMO energy level and disfavored blend film morphology finally limited its solar cell performance to a moderate level (PCE: 3.91%). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 689–698     

Naphthodithiophene‐Diketopyrrolopyrrole‐Based donor–Acceptor alternating π‐Conjugated polymers for Organic thin‐Film transistors

Novel naphtho[1,2‐b:5,6‐b′]dithiophene (NDT) and diketopyrrolopyrrole (DPP)‐containing donor‐acceptor conjugated polymers (PNDTDPPs) with different branched side chains were synthesized via Pd(0)‐catalyzed Stille coupling reaction. Octyldodecyl (OD) and dodecylhexadecyl (DH) groups were tethered to the DPP units as the side chains. The soluble fraction of PNDTDPP‐OD polymer in chloroform has much lower molecular weight than that of PNDTDPP‐DH polymer. PNDTDPP‐DH polymer bearing relatively longer DH side chains exhibited much better charge‐transport behavior than PNDTDPP‐OD polymer with shorter OD side chains. The thermally annealed PNDTDPP‐DH polymer thin films exhibited an outstanding charge carrier mobility of ～1.32 cm² V^?1 s^?1 (I_on/I_off ～ 10⁸) measured under ambient conditions, which is almost six times higher than that of thermally annealed PNDTDPP‐OD polymer thin films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5280–5290     

Influence of fluorination on the microstructure and performance of diketopyrrolopyrrole‐based polymer solar cells

The solar cell performance and microstructure of DPP‐based polymers with different degrees of fluorination are reported. DPP‐based polymers with thiophene–phenyl–thiophene comonomer and thiophene flanking units are studied, with the degree of fluorination of the phenyl unit varied. With bifluorination of the phenyl ring, a higher open circuit voltage is achieved whilst maintaining or even improving the overall solar cell efficiency. While tetrafluorination leads to a further 0.1 V increase in V_OC, reaching a high photo voltage of 0.81 V, overall solar cell performance significantly drops. Microstructural studies using AFM, TEM, Grazing incidence wide‐angle X‐ray scattering (GIWAXS), and Resonant soft X‐ray scattering (R‐SoXS) reveal that bifluorination largely preserves the microstructure of the nonfluorinated system, whereas tetrafluorination results in coarse phase separation between the polymer donor and the fullerene acceptor. Our results demonstrate that the use of an extended comonomer is a promising strategy for optimizing the beneficial effects of fluorination for DPP‐based polymer solar cells, especially in improving the open circuit voltage. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 49–59     

Synthesis,characterizations, and electrochromic properties of donor–acceptor type polymers containing 2, 1, 3‐benzothiadiazole and different thiophene donors

Three donor–acceptor type π‐conjugated monomers containing 2, 1, 3‐benzothiadiazole (Tz) as the acceptor unit and different thiophene derivatives (thiophene, 3,4‐ethylenedioxythiophene, and thieno[3,2‐b]thiophene) as the donor units have been synthesized via Stille coupling reaction. The corresponding polymers are electrochemically deposited onto FTO glass by cyclic voltammetry (CV). The maximum absorption wavelength of the neutral polymers varies with the electron‐rich character of incorporated thiophene moieties, giving rise to tunable colors. In addition, the prepared polymer films demonstrate reasonable transmittance modulation, fast switching rate, high color efficiency and good stability, which meet the requirements of smart windows and electrochromic display applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2239–2246     

Random copolymers based on 3‐hexylthiophene and benzothiadiazole with induced π‐conjugation length and enhanced open‐circuit voltage property for organic photovoltaics

A series of donor‐acceptor low‐bandgap conjugated polymers, that is, HThmBT (m = 3, 6, 9, 12, 15), composed of regioregular 3‐hexylthiophene segments and 2,1,3‐benzothiadiazole units, were synthesized through the Stille coupling polymerization to optimize the π‐conjugation length of the polymer and the intramolecular charge transfer (ICT) effect in the polymer backbone. The polymers had relatively low optical bandgaps ranging from 1.6 to 1.72 eV. Among these polymers, HTh6BT exhibited the best device performance with a power conversion efficiency (PCE) of 1.6%. Moreover, despite being based on thiophene, HTh6BT exhibited a high‐open circuit voltage (V_OC) of over 0.8 V because of its low high occupied molecular orbital (HOMO) energy level. These results provided an effective strategy for designing and synthesizing low‐bandgap conjugated polymers with broad absorption ranges and well‐balanced energy levels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis,photophysics, theoretical modeling,and electroluminescence of novel 2,7‐carbazole‐based conjugated polymers with sterically hindered structures

2,7‐dibromo‐N‐hexylcarbazole is successfully synthesized in three steps with an overall 37% yield. Novel 2,7‐carbazole‐based sterically hindered conjugated polymers are further synthesized. In the backbone structure of polymer P1 , alkylated bithiophene moiety is β‐substituted with dodecyl chains on both thiophene rings, adopting the tail‐to‐tail configuration. While for polymers P2 and P3 , partially planarized thieno[3,2‐b]thiophene moiety ( P2 ) and β‐pentyl substituted thieno[3,2‐b]thiophene ( P3 ) are incorporated. All polymers demonstrate efficient blue‐to‐green light emission, good thermal stability (T_d ≥ 379 °C), and high glass transition temperatures (T_g = 118 °C). The optical and electronic properties of the resulted polymers are tuned by the incorporated alkyl chains. For instance, the incorporation of β‐pentyl group in thieno[3,2‐b]thiophene moiety endows P3 with blue‐shifted photophysical spectra, reduced fluorescence quantum yield and larger band gap in comparison with P2 . The steric effect of incorporated alkyl chains is further illustrated by geometry optimization of three model oligomers (analogues to the repetition units of P1–P3 ) using density functional theory. Sterically hindered polymers P1 and P2 exhibit high charge transport ability and moderate electroluminescent properties in primarily tested single‐layer light‐emitting diodes (configuration: ITO/PEDOT:PSS/Polymer/Ca/Ag). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7725–7738, 2008     

High‐performance amorphous donor–acceptor conjugated polymers containing x‐shaped anthracene‐based monomer and 2,5‐bis(2‐octyldodecyl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione for organic thin‐film transistors

New diketopyrrolopyrrole (DPP)‐containing amorphous conjugated polymers, such as poly(3‐(5‐((9,10‐bis((4‐hexylphenyl)ethynyl)‐6‐(prop‐1‐ynyl)anthracen‐2‐yl)ethynyl) thiophen‐2‐yl)‐5‐(2‐hexyldecyl)‐2‐(2‐octyldodecyl)‐6‐(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) ( 4 ), and poly(3‐(5‐((2,6‐bis((4‐hexylphenyl)ethynyl)‐10‐(prop‐1‐ynyl)anthracen‐9‐yl)ethynyl)thiophen‐2‐yl)‐2,5‐bis(2‐octyldodecyl)‐6‐(thio phen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) ( 7 ), were successfully synthesized via Sonogashira coupling reactions under microwave conditions. Copolymer 7 , incorporating a DPP moiety at the 9,10‐position of the anthracene ring through a triple bond, showed a much lower bandgap energy (E_g = 1.81 eV) than copolymer 4 (E_g = 2.13 eV). Tuning of the molecular frontier orbital energies was achieved by only changing the anchoring position of dithiophenyl‐DPP from the 2,6‐ to the 9,10‐position in the anthracene ring. Because of the donor–acceptor (D–A) interaction and the two‐dimensional planar structure of the X‐shaped donor monomer, the resulting polymers showed good interchain π?π stacking in the thin‐film state, despite being amorphous polymers. When the newly synthesized polymer 7 was used as a semiconductor material in an organic thin‐film transistor, the best mobility of up to 0.12 cm² V^?1 s^?1 (I_on/off = ～ 4.4 × 10⁶) was observed, which is one of the highest values recorded for amorphous polymer films reported to date. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Low band‐gap D–A conjugated copolymers based on anthradithiophene and diketopyrrolopyrrole for polymer solar cells and field‐effect transistors

Two conjugated copolymers PADT‐DPP and PADT‐FDPP based on anthradithiophene and diketopyrrolopyrrole, with thiophene and furan as the π‐conjugated bridge, respectively, were successfully synthesized and characterized. The number‐averaged molecular weights of the two polymers are 38.7 and 30.2 kg/mol, respectively. Polymers PADT‐DPP and PADT‐FDPP exhibit broad absorption bands and their optical band gaps are 1.44 and 1.50 eV, respectively. The highest occupied molecular orbital energy level of PADT‐DPP is located at ?5.03 eV while that of PADT‐FDPP is at ?5.16 eV. In field‐effect transistors, PADT‐DPP and PADT‐FDPP displayed hole mobilities of 4.7 × 10^?3 and 2.7 × 10^?3 cm²/(V s), respectively. In polymer solar cells, PADT‐DPP and PADT‐FDPP showed power conversion efficiency (PCE) of 3.44% and 0.29%, respectively. Atomic force microscopy revealed that the poor efficiency of PADT‐FDPP should be related to the large two‐phase separation in its active layer. If 1,8‐diiodooctane (DIO) was used as the solvent additive, the PCE of PADT‐DPP remained almost unchanged due to very limited morphology variation. However, the addition of DIO could remarkably elevate the PCE of PADT‐FDPP to 2.62% because of the greatly improved morphology. Our results suggest that the anthradithiophene as an electron‐donating polycyclic system is useful to construct new D–A alternating copolymers for efficient polymer solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1652–1661     

Thiophene π bridge effect on bulky side‐chained benzodithiophene‐based photovoltaic polymers

Recently, we have used terthiophene side chain to modify benzo[1,2‐b:4,5‐b′]dithiophene (BDT) to form novel building block for BDT polymers. In this paper, this building block is used to copolymerized with thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) and thieno[3,4‐b]thiophene (TT). This building block and TPD‐ or TT‐based polymers (P1 and P3) show high open circuit voltage (V_OC) (ca. 0.9–0.95 V) and low energy loss (E_g–eV_OC) in solar cells devices compared with similar polymers without bulky side chain. We further introduce thiophene π bridge into these polymers backbone to form two other polymers (P2 and P4). We find this thiophene π bridge does contribute to this bulky side chained benzodithiophene polymer photovoltaic performances, especially for power conversion efficiencies (PCEs). The polymer solar cells (PSCs) performances are moderate in this article due to the serious aggregation in the PSCs active layer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1615–1622     

Synthesis and characterization of new sulfone‐derivatized phenylenevinylene‐based conjugated copolymers with evolving energy levels and gaps

A new series of stable, processable, and chain end functionalizable sulfone‐derivatized phenylenevinylene‐based conjugated polymers (SFPVs) containing different donor type comonomers have been synthesized and characterized. The polymer main chains are consisted of a sulfone‐phenylene electron accepting unit coupled with an electron donating unit which is derived from one of the dialdehyde comonomers based on benzene, thiophene, and pyrrole (with or without alkoxy side chains). The optical energy gaps (E_g) of the new polymers (in solvent) are in a range of 1.9–2.3 eV, with the lowest energy gap obtained from the polymer containing pyrrole as the donor unit. By using a combination of strong donor unit (such as pyrrole) and a relatively weak but stable acceptor unit (sulfone‐substituted benzene), E_g of the conjugated polymers can be tailored to below 2 eV, while the vinylene bonds on the polymer main chain are still chemically stable to survive strong basic conditions as compared with the S,S‐dioxo‐thiophene‐based PTV polymers developed earlier for potential supra‐molecular block copolymer systems. The lowest energy gap P(Pyrrole‐SFPV) exhibited 10 times better photoelectric power conversion efficiency than P(TV‐SFPV). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,solid‐state,and charge‐transport properties of conjugated polythiophene‐S,S‐dioxides

An alkylated semiconducting polymer comprising alternating bithiophene‐[all]‐S,S‐dioxide and aromatic monothiophene units in the polymer backbone was synthesized with the intent of modifying the energy gap and lowest unoccupied molecular orbital for use as a stable n‐type semiconductor. Films spun from this semiconducting polymer were characterized utilizing X‐ray scattering, near edge X‐ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, and thin‐film field effect transistors to determine how oxidation of the thiophene ring systems impacts the structural and electronic properties of the polymer. The thiophene‐S,S‐dioxide polymers have lower optical and electrical band gaps than corresponding thiophene polymers. X‐ray scattering results indicate that the polymers are well ordered with the π–π stacking distances increased by 0.4 Å relative to analogous thiophene polymers. The electrical stability of these polymers is poor in transistors with a drop in the field effect mobility by approximately one order of magnitude upon addition of just 5% of the thiophene‐S,S‐dioxide unit in a copolymer with thiophene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Random multiacceptor poly(2,7‐carbazole) derivatives containing the pentacyclic lactam acceptor unit TPTI for bulk heterojunction solar cells

Here, a family of donor/acceptor (D/A) alternating copolymers and random two‐acceptor and three‐acceptor copolymers were synthesized via Suzuki polymerization based on heptadecan‐9‐yl substituted carbazole as a donor and 4,7‐Bis(5‐bromothiophene‐2‐yl)benzo[c][1,2,5]thiadiazole (DTBT), 2,5‐diethylhexyl‐3,6‐bis(5‐bromothiophene‐2‐yl)pyrrolo[3,4‐c]‐pyrrole‐1,4‐dione (DPP) and 2,8‐dibromo‐4,10‐bis(2‐ethylhexyl)thieno[2′,3′:5,6] pyrido[3,4‐g]thieno[3,2‐c]isoquinoline‐5,11(4H,10H)‐dione (TPTI) as acceptors. For the first time, a relatively new electron‐deficient TPTI unit was used as an acceptor in carbazole‐based conjugated polymers. Introduction of the electron‐deficient TPTI unit into the polymer backbone increased the open‐circuit voltage (V_oc) of the resulting polymer solar cells up to 0.96 V. PCTPTI and PCDTBT‐TPTI exhibited external quantum efficiencies (EQE) up to 75%. All random two‐acceptor copolymers showed broadened absorption profiles compared to the D/A alternating analogues. In order to further improve the light absorption, a random three‐acceptor copolymer was synthesized for the first time, resulting in the broadest absorption in the range of 350–750 nm. Highest occupied molecular orbital (HOMO) energies and V_oc values of the resulting polymers could be successfully tuned by introducing different monomer units into the polymer backbone in different ratios. These results indicate that TPTI is a promising acceptor unit for conjugated polymers and that the random copolymer approach is a successful tool for fine tuning of polymer properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2781–2786     

Synthesis of π‐conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post‐element transformation of organotitanium polymer

The synthesis and unique optoelectronic features of a π‐conjugated polymer containing both thiophene and 1‐phenylphosphole sulfide units (multiple heteroles) in the main chain by the post‐element transformation of a regioregular organometallic polymer possessing titanacyclopentadiene‐2,5‐diyl unit are described. The π‐conjugated polymer containing multiple heteroles was obtained in 73% yield by the simultaneous reaction of the organotitanium polymer with sulfur monochloride and dichlorophenylphosphine (0.6 equiv each), whose number‐average molecular weight (M_n) and the molecular‐weight distribution (M_w/M_n) were estimated to be 11,000 and 3.4, respectively, by the size exclusion chromatography (SEC). The π‐conjugated polymer thus obtained was found to have the high HOMO and the low LUMO energy levels due to the electron‐rich thiophene and electron‐deficient phosphole sulfide units, respectively, as supported by its cyclic voltammetry (CV) analysis. Compared to a mixture of a polymer containing sole thiophene‐unit and that containing sole phosphole sulfide units, the π‐conjugated polymer‐containing multiple heteroles proved to exhibit interesting optical properties. For example, a specific emission peak was observed at 608 nm in the photoluminescence spectrum, which was not observed in the case of the thiophene‐containing polymer, the phosphole‐containing polymer, and their mixture. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2519–2525     

3,6‐Dialkylthieno[3,2‐b]thiophene moiety as a soluble and electron donating unit preserving the coplanarity of photovoltaic low band gap copolymers

It has been shown recently, that the presence of alkyl side chains at the 3‐positions on the thiophene rings placed next to 2,1,3‐benzothiadiazole core in the backbone of several conjugated polymers results in severe steric hindrance and prevents efficient planarity of the thiophene‐2,1,3‐benzothiadiazole‐thiophene (TBzT) segment. Both properties have a strong influence on the optoelectronic properties of the polymer and need to be considered when the polymer is to be used for organic electronics applications. In this work, we modified a previously synthesized oligothiophene copolymer, consisting of two 3,4′‐dialkyl‐2,2′‐bithiophene units attached to a 2,1,3‐benzothiadiazole unit (TBzT segment) and a thieno[3,2‐b]thiophene unit, by optimizing the lateral alkyl side chains following a density functional theory investigation. It is demonstrated that eliminating the alkyl side chains from the 3‐positions of the TBzT segment and anchoring them onto the thieno[3,2‐b]thiophene, using an efficient synthesis of the 3,6‐dihexylthieno[3,2‐b]thiophene unit, allows us to reduce the energy band gap. In addition, the chemical modification leads to a better charge transport and to an enhanced photovoltaic efficiency of polymer/fullerene blends. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Diazaisoindigo bithiophene and terthiophene copolymers for application in field‐effect transistors and solar cells

Two donor–acceptor conjugated polymers with azaisoindigo as acceptor units and bithiophene and terthiophene as donor units have been synthesized by Stille polymerization. These two polymers have been successfully applied in field‐effect transistors and polymer solar cells. By changing the donor component of the conjugated polymer backbone from bithiophene to terthiophene, the density of thiophene in the backbone is increased, manifesting as a decrease in both ionization potential and in electron affinity. Therefore, the charge transport in field‐effect transistors switches from ambipolar to predominantly hole transport behavior. PAIIDTT exhibits hole mobility up to 0.40 cm²/Vs and electron mobility of 0.02 cm²/Vs, whereas PAIIDTTT exhibits hole mobility of 0.62 cm²/Vs. Polymer solar cells were fabricated based on these two polymers as donors with PC₆₁BM and PC₇₁BM as acceptor where PAIIDTT shows a modest efficiency of 2.57% with a very low energy loss of 0.55 eV, while PAIIDTTT shows a higher efficiency of 6.16% with a higher energy loss of 0.74 eV. Our results suggest that azaisoindgo is a useful building block for the development of efficient polymer solar cells with further improvement possibility by tuning the alternative units on the polymer backbone. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2691–2699     

Synthesis of π‐conjugated network polymers based on fluoroarene and fluorescent units via direct arylation polycondensation and their porosity and fluorescent properties

In this study, we report the synthesis of π‐conjugated network polymers including unique fluorescent units via palladium‐catalyzed direct (C? H) arylation polycondensation of 1,2,4,5‐tetrafluorobenzene with tetrabromoarenes. The obtained polymers, including tetraphenylethene (TPE) or pyrene (PYR) units, had microporous structures with the specific Brunauer–Emmett–Teller (BET) surface areas at 508 and 824 m² g^?1, respectively. These polymers possessed narrow pore distributions (<15 nm). These analyses supported that π‐conjugated microporous polymers (CMPs) were synthesized by the direct arylation. Similar to the result of BET surface areas, carbon capture capacity of CMP based on PYR unit was higher than that of CMP based on TPE unit. Because the nitrogen capture capacity of these CMPs was low (≈ 0), selectivity of carbon dioxide adsorption was very high. TPE is a typical aggregation‐induced emission unit but PYR is an aggregation‐caused quenching (ACQ) molecule. The incorporation of TPE unit into the microporous polymer gave green‐colored fluorescence (Φ = 0.12). The polymer including PYR units also showed the green‐colored fluorescence (Φ = 0.05) even though the ACQ property. These synthesized CMPs exhibited characteristic solvatofluorochromism. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3862–3867     

Design and synthesis of dithieno[3,2‐b:2′3′‐d]pyrrole‐based conjugated polymers for photovoltaic applications: consensus between low bandgap and low HOMO energy level

A strategy of the fine‐tuning of the degree of intrachain charge transfer and aromaticity of polymer backbone was adopted to design and synthesize new polymers applicable in photovoltaics. Three conjugated polymers P1 , P2 , and P3 were synthesized by alternating the electron‐donating dithieno[3,2‐b:2′3′‐d]pyrrole (D) and three different electron‐accepting (A) segments ( P1 : N‐(2‐ethylhexyl)phthalimide; P2 : 1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole; and P3 : thiophene‐3‐hexyl formate) in the polymer main chain. Among the three polymers, P2 possessed the broadest absorption band ranging from 300 to 760 nm, the lowest bandgap (1.63 eV), and enough low HOMO energy level (?5.27 eV) because of the strong intrachain charge transfer from D to A units and the appropriate extent of quinoid state in the main chain of P2 , which was convinced by the theoretical simulation of molecular geometry and front orbits. Photovoltaic study of solar cells based on the blends of P1 – P3 and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) demonstrated that P2 :PCBM exhibited the best performance: a power conversion efficiency of 1.22% with a high open‐circuit voltage (V_OC) of 0.70 V and a large short‐circuit current (I_SC) of 5.02 mA/cm² were achieved. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Modular synthesis of polymers containing 2,5‐di(thiophenyl)‐N‐arylpyrrole

A modular and facile route has been developed to synthesize functionalized 2,5‐di(thiophen‐2‐yl)‐1‐H‐arylpyrroles from readily available starting materials. These units are compatible with various polymerization conditions and are versatile building blocks for conjugated polymers. The polymers show high thermal stability and solubility in a number of solvents. Characterization of the polymers reveals a correlation between molecular packing, controllable by polymer design, and charge carrier mobility. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1133–1139     

Silafluorene‐based polymers for electrochromic and polymer solar cell applications

In this study, four novel silafluorene (SiF) and benzotriazole (Btz) bearing conjugated polymers are synthesized. In the context of electrochemical and optical studies, these polymers are promising materials both for electrochromic device (ECD) and polymer solar cell (PSC) applications. All of the polymers are ambipolar (both p‐ and n‐dopable) and multichromic. Electrochemistry experiments indicate that incorporation of selenophene instead of thiophene unit increases the HOMO energy level of the polymers. Power conversion efficiency of the PSCs reached 1.75% for PTBTSiF, 1.55% for PSBSSiF, 2.57% for PBTBTSiF, and 1.82% for PBSBSSiF. The hole mobilities of the polymers are estimated through space charge limited current (SCLC) model. PBTBTSiF has the highest hole mobility as 2.44 × 10^?3 cm² V s^?1. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1541–1547