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Synthesis of novel dithienothiophene- and 2,7-carbazole-based conjugated polymers and H-bonded effects on electrochromic and photovoltaic properties
(2012-12-15)
Fang, Hsiao-Ping
;
Lin, Jia-Wei
;
Chiang, I-Hung
;
Chu, Chih-Wei
;
Wei, Kung-Hwa
Three kinds of dithienothiophene/carbazole-based conjugated polymers (P1P3), which bear acid-protected and benzoic acid pendants in P2 and P3, respectively, were synthesized via Suzuki coupling reaction. Interestingly, P1P3 exhibited reversible electrochromism during the oxidation processes of cyclic voltammogram studies, and P3 (with H-bonds) revealed the best electrochromic property with the most noticeable color change. According to powder X-ray diffraction (XRD) analysis, these polymers exhibited obvious diffraction features indicating bilayered packings between polymer backbones and p-p stacking between layers in the solid state. Compared with the XRD data of P2 (without H-bands), H-bonds of P3 induced a higher crystallinity in the small-angle region (corresponding to a higher ordered bilayered packings between polymer backbones), but with a similar crystallinity in the wide angle region indicating a comparable p-p stacking distance between layers. Moreover, based on the preliminary photovoltaic properties of PSC devices (P1P3 blended individually with PCBM acceptor in the weight ratio of 1:1), P3 (with H-bonds) possessed the highest power conversion efficiency of 0.61% (with Jsc = 2.26 mA/cm2, FF = 29.8%, and Voc = 0.9 V). In contrast to P2 (without H-bands), the thermal stability, crystallinity, and electrochromic along with photovoltaic properties of P3 were generally enhanced due to its H-bonded effects. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
Synthesis of Main-Chain Metallo-Copolymers Containing Donor and Acceptor Bis-Terpyridyl Ligands for Photovoltaic Applications
(2012-04-13)
Padhy, Harihara
;
Ramesh, Mohan
;
Patra, Dhananjaya
;
Satapathy, Rudrakanta
;
Pola, Murali Krishna
Two random (ZnII-based P1P2) and two alternating (RuII-based P3P4) metallo-copolymers containing bis-terpyridyl ligands with various central donor (i.e., fluorene or carbazole) and acceptor (i.e., benzothiadiazole) moieties were synthesized. The effects of electron donoracceptor interactions with metal (ZnII and RuII) ions on their thermal, optical, and electrochemical properties were investigated. Because of the strong ICT transitions between donor and acceptor ligands in both ZnII- and RuII-based metallo-coplymers and MLCT transitions in RuII-based metallo-coplymers, the absorption spectra covered a broad range of 260750 nm with the band gaps of 1.571.77 eV. In addition, the introduction of RuII-based metallo-coplymer P4 mixed with PC60BM as an active layer of the BHJ solar cell device exhibited the highest PCE value up to 0.90%.
Self-Assembly of H-Bonded Side-Chain and Cross-Linking Copolymers Containing Diblock-Copolymeric Donors and Single/Double H-Bonded Light-Emitting Acceptors
(2009-09-15)
Lin, Hong-Cheu
;
Jiang, Meng-Dan
;
Wu, Shen-Chang
;
Jou, Leng-Long
;
Chou, Kai-Pin
A series of diblock-copolymers were synthesized through anionic polymerization of styrene and tert-butyl methacrylate (tBuA) with different monomer ratios, and analogous block-copolymeric derivatives (PS-b-PAA)s with monofunctional carboxylic acid groups were obtained by further hydrolyzation as hydrogen-bonded (H-bonded) proton donors. Via H-bonded interaction, these diblock-coplymeric donors (PS-b-PAA)s were incorporated with luminescent mono-pyridyl/bis-pyridyl acceptors to form single/double H-bonded supramolecules, that is, H-bonded side-chain/cross-linking copolymers, respectively. The supramolecular architectures formed by donor polymers and light-emitting acceptors were influenced by the ratio of acid blocks in the diblock copolymeric donors and the type of single/double H-bonded light-emitting acceptors. Their thermal and luminescent properties can be adjusted by H-bonds, and more than 100 nm of red-shifted photoluminescence (PL) emissions were observed, which depend on the degrees of the H-bonding interactions. Self-assembled phenomena of amphiphilic dibolck copolymers and their H-bonded complexes were confirmed by TEM micrographs, and supramolecular microphase separation of spherical micelle-like morphology was demonstrated to affect the photophysical properties. Polymer light-emitting diode (PLED) devices containing H-bonded complexes showed electroluminescence (EL) emissions of 503-560 nm under turn-on voltages of 7.5-9.0 V, maximum power efficiencies of 0.23-0.37 cd/A (at 100 mA/cm(2)), and maximum luminances of 318-519 cd/m(2) (around 25 V). (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4685-4702, 2009

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