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

A proton–electron
dual-responsive system based on a hybrid
of ferrocene and metalladithiolene (1) was developed.
The formation of the dithiafulvenium moiety was driven by protonation
of the metalladithiolene unit of 1 and by oxidation.
The change in the electronic structure caused by the protonation was
combined with the redox properties of the two components of 1, 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.