Synthesis and Photovoltaic Properties of New Metalloporphyrin-Containing Polyplatinyne Polymers
Synthesis and Photovoltaic Properties of New Metalloporphyrin-Containing Polyplatinyne Polymers
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DOI：
10.1021/ma2006206
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发表时间：
2011-06
期刊：
影响因子：
5.5
通讯作者：
Hongmei Zhan;S. Lamare;A. Ng;T. Kenny;Hannah Guernon;W. Chan;A. Djurišić;P. Harvey;W. Wong
中科院分区：
文献类型：
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作者：
Hongmei Zhan;S. Lamare;A. Ng;T. Kenny;Hannah Guernon;W. Chan;A. Djurišić;P. Harvey;W. Wong
三个新的溶液可加工的铂（II）多炔聚合物含有锌（II）卟啉生色团P1，P2，和P3及其相应的双核模型配合物的合成通过CuI催化的脱卤化氢反应的氯化铂（II）前体和各自的双（乙炔基）-锌（卟啉）金属配体。研究了P1-P3的热、物理（吸收、激发和发射光谱）、电化学和光伏性质。这些结果也相关的含时密度泛函理论（TDDFT）计算。计算证实了在π-系统中存在适度的共轭，对于P3稍微更突出，其中注意到卟啉和噻吩环之间的更有利的二面角。此外，计算的激发态被预测为π-π * 的性质与一些电荷转移组件从trans-C <$CPt（L）2C <$C −] n单元的卟啉环。光学带隙范围从1.93到2.0。
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–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 π-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 π–π* in nature with some charge transfer components from the trans-[−C≡CPt(L)2C≡C−]n unit to the porphyrin rings. The optical bandgaps range from 1.93 to 2.0...