Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.
Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.
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DOI：
10.1038/nchem.2026
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发表时间：
2014-10
期刊：
影响因子：
21.8
通讯作者：
J. Sukegawa;Christina Schubert;Xiaozhang Zhu;H. Tsuji;D. Guldi;E. Nakamura
中科院分区：
文献类型：
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作者：
J. Sukegawa;Christina Schubert;Xiaozhang Zhu;H. Tsuji;D. Guldi;E. Nakamura
电子转移是生物系统、光伏和分子电子学中的一个基本过程。因此，了解分子结构与ET性质之间的关系是非常重要的。为此，人们利用π-共轭分子导线作为桥梁，利用施主-桥-受体分子对光诱导ET进行了广泛的研究。在这里，我们证明了碳桥联的低聚对苯乙炔(COPV)，它既是刚性的，又是平坦的，与同等的柔性分子桥相比，ET速率增加了840倍。由于通过COPV的有效共轭，电子给体和电子受体之间的电子耦合增强，从而使速率提高了120倍。其余的速率增强可以用电子-振动耦合引起的非弹性电子隧穿COPV来解释，这在室温下有机分子导线的溶液中是前所未有的。这种类型的非线性效应显示了COPV在分子器件应用中的多功能性和潜在的实用价值。
Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor–bridge–acceptor molecules, in whichπ-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron–vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.