Publication

Synthetic, structural, spectroscopic and theoretical study of a mn(iii)–cu(ii) dimer containing a jahn–teller compressed mn ion

Berg, Nelly
Hooper, Thomas N.
Liu, Junjie
Beedle, Christopher C.
Singh, Saurabh Kumar
Rajaraman, Gopalan
Piligkos, Stergios
Hill, Stephen
Brechin, Euan K.
Jones, Leigh F.
Citation
Berg, Nelly; Hooper, Thomas N. Liu, Junjie; Beedle, Christopher C.; Singh, Saurabh Kumar; Rajaraman, Gopalan; Piligkos, Stergios; Hill, Stephen; Brechin, Euan K.; Jones, Leigh F. (2013). Synthetic, structural, spectroscopic and theoretical study of a mn(iii)–cu(ii) dimer containing a jahn–teller compressed mn ion. Dalton Trans. 42 (1), 207-216
Abstract
The heterobimetallic complex [Cu(II)Mn(III)(L)(2)(py)(4)](ClO4)center dot 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 D-Mn(III) = +4.45 cm(-1). DFT calculations also yield an antiferromagnetic exchange for 1, though the magnitude is overestimated (J(DFT) = -71 cm(-1)). Calculations reveal that the antiferromagnetic interaction essentially stems from the Mn(d(x2-y2))-Cu(d(x2-y2)) 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.
Funder
Publisher
Royal Society of Chemistry (RSC)
Publisher DOI
10.1039/c2dt31995k
Rights
Attribution-NonCommercial-NoDerivs 3.0 Ireland