title: A single molecular system gating electron transfer by ring inversion of a methylpyridylpyrimidine ligand on copper.
abstract: We have succeeded in constructing an electron-transfer gating system involving a copper complex, 1.BF(4), that is regulated by the rotational motion of a pyridylpyrimidine ligand. 4-Methyl-2-(2'-pyridyl)pyrimidine confined between two bulky groups underwent a dynamic process derived from pyrimidine-ring coordination inversion between inner and outer isomers, and these isomers interconverted with each other in solution with a barrier of 73 kJ mol(-1) at 293 K. As the ring-inversion process induces a change in redox potential on the copper center, electron transfer between 1(+) and the electrode can be gated through on/off control of the inversion by changing the temperature, resulting in a -0.14 V shift of the electrode potential.
authors.affiliation: Department of Chemistry, Graduate school of Science, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Kuniharu
authors.initials: K
authors.lastname: Nomoto
authors.forename: Shoko
authors.initials: S
authors.lastname: Kume
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara