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

Kelsey, Shaun R.; Kumar, Amit; Oliver, Allen G.; Day, Victor W.; Blakemore, James D.

doi:10.1002/celc.202100358

Title: Promotion and Tuning of the Electrochemical Reduction of Hetero‐ and Homobimetallic Zinc Complexes**

Journal Article · Mon Aug 02 00:00:00 EDT 2021 · ChemElectroChem

DOI:https://doi.org/10.1002/celc.202100358· OSTI ID:1785556

Kelsey, Shaun R. ^[1]; Kumar, Amit ^[1]; Oliver, Allen G. ^[2]; Day, Victor W. ^[1];

^[1]

Department of Chemistry University of Kansas 1567 Irving Hill Rd Lawrence KS 66045
Department of Chemistry and Biochemistry University of Notre Dame 149 Stepan Chemistry Notre Dame IN 46556 USA

Abstract Compounds containing multiple metals attract significant interest due to the useful redox and reactivity properties of such species. Here, the electrochemical properties of a family of macrocyclic complexes that feature a zinc(II) center paired with a secondary redox‐inactive metal cation in heterobimetallic (Na ⁺ , Ca ²⁺ , Nd ³⁺ , Y ³⁺ ) motifs or homobimetallic (Zn ²⁺ ) motifs have been investigated. The new complexes were prepared via a divergent strategy, isolated, and structurally characterized with single‐crystal X‐ray diffraction (XRD) analysis. XRD results show that the structures of the complexes are modulated by the identity of the incorporated secondary metal ions. Cyclic voltammetry data reveal that ligand‐centered reduction is promoted in the bimetallic complexes and that the paired metal ions synergistically influence the redox properties of the complexes. Similar to prior work from our group and others, the bimetallic complexes containing stronger Lewis acids undergo more significant reduction potential shifts; contrasting with prior work on complexes containing redox‐active metals, however, the zinc(II) complexes studied here display faster electron transfer (as judged by lower reorganization energies, λ) when incorporating di‐ or tri‐valent Lewis acids in contrast to monovalent (and more weakly acidic) sodium. The quantified trends in these data offer insights that could help distinguish metal‐ versus ligand‐centered reduction of bimetallic complexes.

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Sponsoring Organization:: USDOE

OSTI ID:: 1785556

Journal Information:: ChemElectroChem, Journal Name: ChemElectroChem Vol. 8 Journal Issue: 15; ISSN 2196-0216

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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