Modulation of Energy Conversion Processes in Carbonaceous Molecular Bearings
Modulation of Energy Conversion Processes in Carbonaceous Molecular Bearings
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DOI：
10.1002/asia.201500673
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发表时间：
2015-11-01
影响因子：
4.1
通讯作者：
Isobe, Hiroyuki
中科院分区：
文献类型：
--
作者：
Hitosugi, Shunpei;Ohkubo, Kei;Isobe, Hiroyuki
研究了具有离散分子结构的碳质分子轴承的能量学和光动力学性质。一系列超分子轴承，包括带持久型管状环芳烃和富勒烯分子，通过光诱导电子转移过程接受光子刺激，提供电荷分离物种。然而，与光激发相关的能量转换过程因分子结构的不同而不同。加长的管状分子允许在轴承处出现中间三重态激发态，这应该会导致能量转换为热能。另一方面，富勒烯中的面内锂离子诱导的低位电荷分离物种使反向电子转移过程得以发生，而不涉及三重态激发物种。根据马库斯理论分析了结构-光动力学关系，揭示了该动态超分子体系中的大的电子耦合。
The energetics and photodynamics of carbonaceous molecular bearings with discrete molecular structures were investigated. A series of supramolecular bearings comprising belt-persistent tubular cycloarylene and fullerene molecules accepted photonic stimuli to afford charge-separated species via a photoinduced electron transfer process. The energy conversion processes associated with the photoexcitation, however, differed depending on the molecular structure. A -lengthened tubular molecule allowed for the emergence of an intermediary triplet excited state at the bearing, which should lead to an energy conversion to thermal energy. On the other hand, low-lying charge-separated species induced by an endohedral lithium ion in fullerene enabled back electron transfer processes to occur without involving triplet excited species. The structure-photodynamics relationship was analyzed in terms of the Marcus theory to reveal a large electronic coupling in this dynamic supramolecular system.