Spin-Reconstructed Proton-Coupled Electron Transfer in a Ferrocene–Nickeladithiolene Hybrid

Abstract

A proton–electron dual-responsive system based on a hybrid of ferrocene and metalladithiolene (<b>1</b>) was developed. The formation of the dithiafulvenium moiety was driven by protonation of the metalladithiolene unit of <b>1</b> and by oxidation. The change in the electronic structure caused by the protonation was combined with the redox properties of the two components of <b>1</b>, generating two radical species with different spin density distributions (3d spin and π spin). Furthermore, a spin-reconstructed proton-coupled electron transfer, i.e., the transformation from 3d spin to π spin accompanied by deprotonation, was achieved by a temperature change, the third external stimulus