Effect of dual fullerenes on lifetimes of charge-separated states of subphthalocyanine-triphenylamine-fullerene molecular systems
Effect of dual fullerenes on lifetimes of charge-separated states of subphthalocyanine-triphenylamine-fullerene molecular systems
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DOI：
10.1021/jp7108658
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发表时间：
2008-04-03
影响因子：
3.3
通讯作者：
Kay, Kwang-Yol
中科院分区：
文献类型：
--
作者：
E-Khouly, Mohamed E.;Shim, Sun Hee;Kay, Kwang-Yol
研究了新合成的亚酞菁-三苯胺-富勒烯三元组（SubPc-TPA-C-60）和亚酞菁-三苯胺-双富勒烯四元组（SubPc-TPA-（C-60）（2））的光诱导分子内电子转移事件。采用从头计算B3 LYP/3- 21 G方法对该三元组的几何结构和电子结构进行了研究，预测SubPc-TPA（中心点+）-C-60（中心点-）为稳定的电荷分离态.通过激发单重态的SubPc的光诱导事件进行了监测，通过时间分辨的发射测量以及瞬态吸收技术。通过SubPc的激发态观察到有效的电荷分离，速率接近10（10）s（-1）。与SubPc-TPA二元体相比，SubPc-TPA-C-60三元体在苯甲腈溶液中具有长寿命的电荷分离态，其自由基离子对寿命（tau（RIP））为670 ns.有趣的是，在SubPc-TPA-（C-60）（2）的电荷分离状态下实现了进一步的电荷稳定，其中发现在苯甲腈中的TRIP为1050 ns。
Photoinduced intramolecular electron-transfer events of the newly synthesized subphthalocyanine-triphenylamine-fullerene triad (SubPc-TPA-C-60) and subphthalocyanine-triphenylamine-bisfullerene tetrad (SubPc-TPA-(C-60)(2)) were studied. The geometric and electronic structures of the triad were probed by ab initio B3LYP/3-21G method, which predicts SubPc-TPA(center dot+)-C-60(center dot-) as a stable charge-separated state. The photoinduced events via the excited singlet state of SubPc were monitored by time-resolved emission measurements as well as transient absorption techniques. Efficient charge-separations via the excited states of SubPc were observed with the rates of similar to 10(10) s(-1). Compared with the SubPc-TPA dyad, a long-lived charge-separated state was observed for the SubPc-TPA-C-60 triad with the lifetime of the radical ion pairs (tau(RIP)) of 670 ns in benzonitrile. Interestingly, further charge stabilization was achieved in the charge-separated state of SubPc-TPA-(C-60)(2), in which the TRIP was found to be 1050 ns in benzonitrile.