Valence tautomerism in a [2 × 2] Co4 grid complex containing a ditopic arylazo ligand

Nico M Bonanno; Zackery Watts; Cole Mauws; Brian O Patrick; Christopher R Wiebe; Yuki Shibano; Kenji Sugisaki; Hideto Matsuoka; Daisuke Shiomi; Kazunobu Sato; Takeji Takui; Martin T Lemaire

doi:10.1039/d1cc01991k

Valence tautomerism in a [2 × 2] Co₄ grid complex containing a ditopic arylazo ligand

Chem Commun (Camb). 2021 Jun 22;57(50):6213-6216. doi: 10.1039/d1cc01991k.

Authors

Affiliations

¹ Department of Chemistry, Brock University, St. Catharines, ON L2S 3A1, Canada. mlemaire@brocku.ca.
² Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada.
³ Department of Chemistry, University of British of Columbia, Vancouver, BC V6T 1Z1, Canada.
⁴ Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada and Department of Chemistry, University of Winnipeg, Winnipeg, MB R3B 2E9, Canada.
⁵ Department of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Osaka 558 8585, Japan.

PMID: 34059865
DOI: 10.1039/d1cc01991k

Abstract

We describe the structural and magnetic properties of a tetranuclear [2 × 2] Co4 grid complex containing a ditopic arylazo ligand. At low temperatures and in solution the complex is comprised of Co3+ and singly reduced trianion-radical ligands. In the solid state we demonstrate the presence of valence tautomerization via variable temperature magnetic susceptibility experiments and powder-pattern EPR spectroscopy. Valence tautomerism in polynuclear complexes is very rare and to our knowledge is unprecedented in [2 × 2] grid complexes.