Intramolecular electron arrangement with a rotative trigger.

We have constructed a single molecule system, consisting of a ferrocene-tethered copper complex, in which electron transfer between redox centers is triggered by molecular rotational motion. In the compound, an asymmetric methyl-substituted 2,2'-pyridylpyrimidine ligand, tethered to the ferrocene moiety, has two isomeric ring-inversion coordination conformations around the copper center. Both isomeric structures were characterized by X-ray crystallography. (1)H NMR and electrochemical measurements revealed that these isomers interconvert through rotation of the pyrimidine at room temperature, but the process is frozen below 233 K in the solution state. The two isomers undergo different redox processes, and the identity of the first oxidation center alternates between the copper center and ferrocene, as confirmed by chemical oxidation monitored by EPR and UV-vis absorption spectroscopy. Oxidation of the compound causes spontaneous isomerization of the pyrimidine due to the different relative stabilities of the isomers in the monovalent and divalent states. Oxidation in the motionless state at low temperatures extracts the first electron from the ferrocene center. When molecular motion is released by warming, the electron moves from the copper center to the ferrocene, leading to an enhancement of the copper(II) signal in the EPR spectrum. The synchronized motion/electron migration process was observed as a one-step UV-vis absorption spectral conversion.