Synthesis and Photovoltaic Properties of New Metalloporphyrin-Containing Polyplatinyne Polymers
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- 作者：Hongmei Zhan ; Simon Lamare ; Annie Ng ; Tommy Kenny ; Hannah Guernon ; Wai-Kin Chan ; Aleksandra B. Djuris虒ic虂 ; Pierre D. Harvey ; Wai-Yeung Wong
- 刊名：Macromolecules
- 出版年：2011
- 出版时间：July 12, 2011
- 年：2011
- 卷：44
- 期：13
- 页码：5155-5167
- 全文大小：1223K
- 年卷期：v.44,no.13(July 12, 2011)
- ISSN：1520-5835
文摘
Three new solution-processable platinum(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鈥?b>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 蟺-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 蟺鈥撓€* in nature with some charge transfer components from the trans-[鈭扖鈮Pt(L)2C鈮鈭抅n unit to the porphyrin rings. The optical bandgaps range from 1.93 to 2.02 eV for P1鈥?b>P3. Intense 蟺鈥撓€*-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 蟺-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鈥? and fill factor of 0.39 under illumination of an AM 1.5 solar cell simulator.