期刊
MACROMOLECULES
卷 44, 期 13, 页码 5155-5167出版社
AMER CHEMICAL SOC
DOI: 10.1021/ma2006206
关键词
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资金
- Hong Kong Research Grants Council [HKBU 202607, HKUST2/CRF/10]
- Hong Kong Baptist University [FRG2/09-10/091]
- Croucher Foundation
- University Grants Committee, Hong Kong [AoE/P-03/08]
- University of Hong Kong
Three new solution-processable platimun(II) polyyne polymers containing zinc(II) porphyrinate chromophores P1, P2, and P3 and their corresponding dinuclear model complexes were synthesized via the CuI-catalyzed dehydrohalogenation reaction of the platinum(II) chloride precursor and each of the respective bis(ethynyl)-zinc(porphyrin) metalloligands. The thermal, photophysical (absorption, excitation and emission spectra), electrochemical, and photovoltaic properties of P1-P3 were investigated. These results are also correlated by time-dependent density functional theory (TDDFT) calculations. The computations corroborate the presence of moderate conjugation in the it-systems, somewhat more accentuated for P3 where more favorable dihedral angles between the porphyrin and thiophene rings are noted. Moreover, the computed excited states are predicted to be pi-pi* in nature with some charge transfer components from the trans-[-C CPt(L)(2)C C-](n) unit to the porphyrin rings. The optical bandgaps range from 1.93 to 2.02 eV for P1-P3. Intense pi-pi*-localized fluorescence emissions typical of the Q-bands of the polymers were observed. The effect of thiophene ring along the polymer chain on the extent of pi-conjugation, luminescent and photovoltaic properties of these metalated materials was also examined. Bulk heterojunction solar cells using these metallopolymers as an electron donor blended with a methanofullerene electron acceptor were studied. In one case, the metallopolymer P3 showed a power conversion efficiency of 1.04% with the open-circuit voltage of 0.77 V, short-circuit current density of 3.42 mA cm(-2) and fill factor of 0.39 under illumination of an AM 1.5 solar cell simulator.
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