Synthetic, structural, spectroscopic and theoretical study of a Mn(iii)-Cu(ii) dimer containing a Jahn-Teller compressed Mn ion

Nelly Berg, Thomas N. Hooper, Junjie Liu, Christopher C. Beedle, Saurabh Kumar Singh, Gopalan Rajaraman, Stergios Piligkos, Stephen Hill, Euan K. Brechin, Leigh F. Jones

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

The heterobimetallic complex [Cu(ii)Mn(iii)(L)2(py) 4](ClO4)·EtOH (1) built using the pro-ligand 2,2′-biphenol (LH2), contains a rare example of a Jahn-Teller compressed Mn(iii) centre. Dc magnetic susceptibility measurements on 1 reveal a strong antiferromagnetic exchange between the Cu(ii) and Mn(iii) ions mediated through the phenolate O-atoms (J = -33.4 cm-1), with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high-field and high frequency powder EPR data suggest a single-ion anisotropy DMn(III) = +4.45 cm-1. DFT calculations also yield an antiferromagnetic exchange for 1, though the magnitude is overestimated (JDFT = -71 cm-1). Calculations reveal that the antiferromagnetic interaction essentially stems from the Mn(dx2-y2)-Cu(dx2-y 2) interaction. The computed single-ion anisotropy and cluster anisotropy also correlates well with experiment. A larger cluster anisotropy for the S = 3/2 state compared to the single-ion anisotropy of Mn(iii) is rationalised on the basis of orbital mixing and various contributions that arise due to the spin-orbit interaction.

Original languageEnglish (US)
Pages (from-to)207-216
Number of pages10
JournalDalton Transactions
Volume42
Issue number1
DOIs
StatePublished - Jan 7 2013

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