Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes

Andrew Barker; Conor T. Kelly; Irina A. Kühne; Stephen Hill; J. Krzystek; Paul Wix; Kane Esien; Solveig Felton; Helge Müller-Bunz; Grace G. Morgan

doi:10.1039/C9DT02476J

Spin state solvomorphism in a series of rare S = 1 manganese(iii) complexes†

Andrew Barker,‡^a Conor T. Kelly,

‡^a Irina A. Kühne,

^a Stephen Hill,

^bc J. Krzystek,

^b Paul Wix,

^d Kane Esien,^e Solveig Felton,

^e Helge Müller-Bunz^a and Grace G. Morgan

*^a

Author affiliations

* Corresponding authors

^a School of Chemistry, University College Dublin (UCD), Belfield, Dublin 4, Ireland
E-mail: grace.morgan@ucd.ie

^b National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA

^c Department of Physics, Florida State University, Tallahassee, FL 32306, USA

^d School of Chemistry & CRANN Institute, Trinity College Dublin, University of Dublin, College Green, Dublin 2, Ireland

^e Centre for Nanostructured Media (CNM), School of Mathematics and Physics, Queen's University Belfast, Belfast, BT7 1NN, UK

Abstract

Structural, magnetic and spectroscopic data of four complex salts, [Mn(napsal₂323)]NTf₂, 1,[Mn(napsal₂323)]ClO₄, 2, [Mn(napsal₂323)]BF₄, 3 and [Mn(napsal₂323)]NO₃, 4, of the [Mn(napsal₂323)]⁺ complex cation indicate that the Mn³⁺ ion is stabilized in the rare S = 1 spin triplet form in this ligand sphere. Zero-field splitting values of D = +19.6 cm⁻¹ and |E| = 2.02 cm⁻¹ for complex 1 were obtained by High Field Electron Paramagnetic Resonance (HFEPR) measurements conducted over a range of frequencies. Structural and magnetic data also indicate that co-crystallization of complexes 2 and 3 with 0.5 equivalents of ethanol yields the high spin S = 2 forms of the perchlorate and tetrafluoroborate solvates [Mn(napsal₂323)]ClO₄·0.5(C₂H₅OH), 2·0.5EtOH and [Mn(napsal₂323)]BF₄·0.5(C₂H₅OH), 3·0.5EtOH.

This article is part of the themed collection: Modern coordination chemistry

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Spin state solvomorphism in a series of rare S = 1 manganese(iii) complexes†

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