Weiss Emily A, Ahrens Michael J, Sinks Louise E, Gusev Alexey V, Ratner Mark A, Wasielewski Michael R
Center for Nanofabrication and Molecular Self-Assembly, Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA.
J Am Chem Soc. 2004 May 5;126(17):5577-84. doi: 10.1021/ja0398215.
Functional molecular wires are essential for the development of molecular electronics. Charge transport through molecules occurs primarily by means of two mechanisms, coherent superexchange and incoherent charge hopping. Rates of charge transport through molecules in which superexchange dominates decrease approximately exponentially with distance, which precludes using these molecules as effective molecular wires. In contrast, charge transport rates through molecules in which incoherent charge hopping prevails should display nearly distance independent, wirelike behavior. We are now able to determine how each mechanism contributes to the overall charge transport characteristics of a donor-bridge-acceptor (D-B-A) system, where D = phenothiazine (PTZ), B = p-oligophenylene, and A = perylene-3,4:9,10-bis(dicarboximide) (PDI), by measuring the interaction between two unpaired spins within the system's charge separated state via magnetic field effects on the yield of radical pair and triplet recombination product.
功能性分子导线对于分子电子学的发展至关重要。电荷通过分子的传输主要通过两种机制进行,即相干超交换和非相干电荷跳跃。在超交换占主导的分子中,电荷传输速率随距离大致呈指数下降,这使得这些分子无法用作有效的分子导线。相比之下,在非相干电荷跳跃占主导的分子中,电荷传输速率应表现出几乎与距离无关的线状行为。我们现在能够通过测量磁场对自由基对和三重态复合产物产率的影响,来确定每种机制如何对供体-桥-受体(D-B-A)系统的整体电荷传输特性做出贡献,其中D = 吩噻嗪(PTZ),B = 对-低聚亚苯基,A = 苝-3,4:9,10-双(二甲酰亚胺)(PDI)。