Three site molecular orbital controlled single-molecule rectifiers based on perpendicularly linked porphyrin-imide dyads
Three site molecular orbital controlled single-molecule rectifiers based on perpendicularly linked porphyrin-imide dyads
复制标题
基于垂直连接的卟啉-酰亚胺二元体的三位点分子轨道控制的单分子整流器
DOI：
10.1039/c9nr07105a
复制
发表时间：
2019
期刊：
影响因子：
6.7
通讯作者：
Ogawa Takuji
中科院分区：
文献类型：
--
作者：
Handayani Murni;Tanaka Hirofumi;Katayose Shinichi;Ohto Tatsuhiko;Chen Zhijin;Yamada Ryo;Tada Hirokazu;Ogawa Takuji
最初由Aviram和Ratner提出的单分子整流器是基于供体- σ-受体结构，其中σ作为绝缘体断开两部分的π电子系统。然而，目前还没有实验证明基于这种机制的高效单分子整流器的报道。在本文中，我们展示了垂直连接的金属卟啉-亚胺二元结构的单分子整流器。我们提出的分子整流器在两端使用羟基作为弱锚定基团。对这些分子的单分子电流-电压特性的测量清楚地表明，整流比平均达到了14的高值。此外，该比率可以通过改变卟啉核心中的中心金属来调节。所有这些特征都可以用分子轨道的能级位移来解释，用一个有三个电子部分的模型。
The original single-molecule rectifier proposed by Aviram and Ratner is based on a donor–σ-acceptor structure, in which σ functions as the insulator to disconnect the π electronic systems of the two parts. However, there have been no reports on experimentally demonstrated highly efficient single-molecule rectifiers based on this mechanism. In this paper, we demonstrate single-molecule rectifiers with perpendicularly connected metal porphyrin–imide dyads. Our proposed molecule rectifiers use hydroxyl groups at both ends as weak anchoring groups. Measurements of the single-molecule current–voltage characteristics of these molecules clearly show that the rectification ratio reached a high value of 14 on average. Moreover, the ratio could be tuned by changing the central metal in the porphyrin core. All of these features can be explained by the energy-level shift of the molecular orbital using a model with three electronic parts.