title: Molecular Rectification Tuned by Through-Space Gating Effect.
abstract: 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.
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Na
authors.identifier: 0000-0001-7680-0504
authors.initials: N
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Wai-Yip
authors.identifier: 0000-0002-5171-2564
authors.initials: WY
authors.lastname: Lo
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Zhengxu
authors.identifier: 0000-0003-0239-9601
authors.initials: Z
authors.lastname: Cai
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Lianwei
authors.identifier: 0000-0002-1996-6046
authors.initials: L
authors.lastname: Li
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Luping
authors.initials: L
authors.lastname: Yu
keywords: Molecular diode; STM-BJ; rectification; through-space gate