Bridged cyclometalated diruthenium complexes for fundamental electron transfer studies and multi-stage redox switching.

Four bridged cyclometalated diruthenium systems are highlighted in this Frontier article, including strongly-coupled diruthenium complexes with a short phen-1,4-diyl or a planar pyren-2,7-diyl bridge, redox asymmetric diruthenium complexes characterized by different terminal ligands on the two ends, diruthenium complexes with a urea bridge that allows modulating the degree of electronic coupling, and those with a redox-active amine bridge with varying electronic structures. These complexes posess redox couples with low potentials and intense intervalence charge transfer absorptions in the near-infrared region in the one-electron-oxidized mixed-valent state. They are appealing not only for providing a platform for fundamental electron transfer studies but also as molecular materials with multi-stage redox switching properties.