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†

Nico M. Bonanno,^a Zackery Watts,^a Cole Mauws,

^b Brian O. Patrick,^c Christopher R. Wiebe,

^bd Yuki Shibano,^e Kenji Sugisaki,

*^e Hideto Matsuoka,

^e Daisuke Shiomi,

^e Kazunobu Sato,

*^e Takeji Takui

*^e and Martin T. Lemaire

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, Brock University, St. Catharines, ON, Canada
E-mail: mlemaire@brocku.ca

^b Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada

^c Department of Chemistry, University of British of Columbia, Vancouver, BC, Canada

^d Department of Chemistry, University of Winnipeg, Winnipeg, MB, Canada

^e Department of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, Osaka 558 8585, Japan

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.

Chemical Communications

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

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

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