Coordination Environment Prevents Access to Intraligand Charge-Transfer States through Remote Substitution in Rhenium(I) Terpyridinedicarbonyl Complexes

Abstract

Six rhenium(I) κ3N-dicarbonyl complexes with 4′-(4-substituted phenyl)terpyridine ligands were evaluated in their ground and excited states. These complexes, bearing substituents of different electron-donating strengths—from CN to NMe2—were studied by a combination of transient IR (TRIR), electrochemistry, and IR spectroelectrochemistry, as well as time-dependent density functional theory (TD-DFT). They exhibit panchromatic absorption and can act as stronger photoreductants than their tricarbonyl counterparts. The ground- and excited- Show more