Promotion and Tuning of the Electrochemical Reduction of Hetero? and Homobimetallic Zinc Complexes**

Compounds containing multiple metals attract significant interest due to the useful redox and reactivity properties of such species. Here, electrochemical a family macrocyclic complexes that feature zinc(II) center paired with secondary redox-inactive metal cation in heterobimetallic (Na+, Ca2+, Nd3+, Y3+) motifs or homobimetallic (Zn2+) have been investigated. The new were prepared via divergent strategy, isolated, structurally characterized single-crystal X-ray diffraction (XRD) analysis. XRD results show structures are modulated by identity incorporated ions. Cyclic voltammetry data reveal ligand-centered reduction is promoted bimetallic ions synergistically influence complexes. Similar prior work from our group others, stronger Lewis acids undergo more potential shifts; contrasting on redox-active metals, however, studied here display faster electron transfer (as judged lower reorganization energies, ?) when incorporating di- tri-valent contrast monovalent (and weakly acidic) sodium. quantified trends these offer insights could help distinguish metal- versus