Electronic Modulation of the SOMO-HOMO Energy Gap in Iron(III) Complexes towards Unimolecular Current Rectification

摘要

Amphiphilic five-coordinate iron(III) complexes with {N2O2Cl} and {N2O3} coordination spheres are studied to elucidate the roles of electronic structure on the mechanisms for current rectification. The presence of an apical chlorido or phenolato ligand plays a crucial role, and the Fe-III{N2O2Cl} species supports an asymmetric mechanism while its Fe-III{N2O3} counterpart seems to allow for unimolecular mechanism. The effects of electron-donating and electron-withdrawing substituents in the ligand frameworks are also considered.