Influence of internal electrostatics on reduction potentials in amine-ligated bimetallic copper complexes

Abstract

The electrostatic modulation of redox potentials of molecular electrocatalysts is a promising strategy to minimize overpotentials without compromising their catalytic activity given their intrinsic correlation. While the introduction of s-block cations to modulate the redox potential of single-site transition metal catalysts is known, the prevalence and nature of such electrostatic interactions in bimetallic complexes deserves further attention. In this work, using density functional theory and electrostatic charged sphere models, we quantify the influence of distance-dependent electrostatic effects on the reduction potentials of a bimetallic Cu(II) model system with a dipicolylamine (DPA) ligand, wherein the Cu(II) centers are bridged by an aliphatic diamine (NH₂-(CH₂)_n-NH₂) linker of varying chain lengths (n = 0 to 10). The calculated reduction potentials in non-aqueous solvation environments were found to vary linearly with the reciprocal of the Cu–Cu distance with a slope of 4.1 V Å, and span more than 500 mV, suggesting a strong distance-dependent coulombic electrostatic interaction between the two metal centers. The effect of chemical perturbations to the primary coordination sphere on the distance-dependent electrostatic effects, viz. nature of the metal ion, overall charge and ligand field, was quantified. The in silico predicted shifts in the one-electron redox potential as a function of the chain length in the model system were experimentally validated with the synthesis and cyclic voltammetry studies of two bimetallic Cu(II)(DPA) complexes bridged by 1,4-diaminobutane and 1,8-diaminooctane in acetonitrile.