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

Dalton Trans. 2019 Nov 7;48(41):15560-15566. doi: 10.1039/c9dt02476j. Epub 2019 Jul 25.

Authors

Affiliations

¹ School of Chemistry, University College Dublin (UCD), Belfield, Dublin 4, Ireland. grace.morgan@ucd.ie.
² National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA and Department of Physics, Florida State University, Tallahassee, FL 32306, USA.
³ National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA.
⁴ School of Chemistry & CRANN Institute, Trinity College Dublin, University of Dublin, College Green, Dublin 2, Ireland.
⁵ Centre for Nanostructured Media (CNM), School of Mathematics and Physics, Queen's University Belfast, Belfast, BT7 1NN, UK.

PMID: 31342029
DOI: 10.1039/c9dt02476j

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.