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

We describe the structural and magnetic properties of a tetranuclear [2 × 2] Co 4 grid complex containing a ditopic arylazo ligand. At low temperatures and in solution the complex is comprised of Co 3+ and singly reduced trianion-radical ligands. In the solid state we demonstrate the presence of val...

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Published inChemical communications (Cambridge, England) Vol. 57; no. 5; pp. 6213 - 6216
Main Authors Bonanno, Nico M, Watts, Zackery, Mauws, Cole, Patrick, Brian O, Wiebe, Christopher R, Shibano, Yuki, Sugisaki, Kenji, Matsuoka, Hideto, Shiomi, Daisuke, Sato, Kazunobu, Takui, Takeji, Lemaire, Martin T
Format Journal Article
Published 22.06.2021
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Summary:We describe the structural and magnetic properties of a tetranuclear [2 × 2] Co 4 grid complex containing a ditopic arylazo ligand. At low temperatures and in solution the complex is comprised of Co 3+ 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. A [2 × 2] cobalt grid complex containing a ditopic arylazo trianion-radical ligand is shown to exhibit valence tautomerism in the solid state.
Bibliography:Electronic supplementary information (ESI) available: Synthetic details, spectroscopic, electrochemical, computational and single crystal X-ray data (PDF). CCDC
For ESI and crystallographic data in CIF or other electronic format see DOI
10.1039/d1cc01991k
1922364
and
1922365
ISSN:1359-7345
1364-548X
DOI:10.1039/d1cc01991k