Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
Nano Lett. 2017 Jan 11;17(1):308-312. doi: 10.1021/acs.nanolett.6b04110. Epub 2016 Dec 7.
Inspired by transistors and electron transfer in proteins, we designed a group of pyridinoparacyclophane based diodes to study the through-space electronic gating effect on molecular rectification. It was shown that an edge-on gate effectively tunes the rectification ratio of a diode via through-space interaction. Higher rectification ratio was obtained for more electron-rich gating groups. The transition voltage spectroscopy showed that the forward transition voltage is correlated to the Hammett parameter of the gating group. Combining theoretical calculation and experimental data, we proposed that the change in rectification was induced by a shift in HOMO level both spatially and energetically. This design principle based on through-space edge-on gate is demonstrated on molecular wires, switches, and now diodes, showing the potential of molecular design in increasing the complexity of single-molecule electronic devices.
受晶体管和蛋白质中电子转移的启发，我们设计了一组基于吡啶并对环芳烷的二极管，以研究对分子整流的空间电子门控效应。结果表明，沿面门控通过空间相互作用有效地调节了二极管的整流比。具有更多富电子门控基团的二极管获得了更高的整流比。过渡电压光谱表明，正向过渡电压与门控基团的哈米特参数相关。结合理论计算和实验数据，我们提出整流的变化是由 HOMO 能级在空间和能量上的移动引起的。这种基于空间沿面门控的设计原理已在分子线、开关上得到了验证，现在又在二极管上得到了验证，展示了分子设计在增加单分子电子器件复杂性方面的潜力。
