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

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Title Synthetic, structural, spectroscopic and theoretical study of a Mn(III)-Cu(II) dimer containing a Jahn-Teller compressed Mn ion
 
Creator BERG, N
HOOPER, TN
LIU, JJ
BEEDLE, CC
SINGH, SK
RAJARAMAN, G
PILIGKOS, S
HILL, S
BRECHIN, EK
JONES, LF
 
Subject SINGLE-MOLECULE MAGNETS
TRANSITION-METAL-COMPLEXES
EXCHANGE COUPLING-CONSTANTS
DENSITY-FUNCTIONAL THEORY
HIGH-FIELD EPR
CHAIN MAGNETS
MANGANESE CLUSTER
HIGH-FREQUENCY
BASIS-SETS
CU
 
Description 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.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-17T04:51:41Z
2014-10-17T04:51:41Z
2013
 
Type Article
 
Identifier DALTON TRANSACTIONS, 42(1)207-216
http://dx.doi.org/10.1039/c2dt31995k
http://dspace.library.iitb.ac.in/jspui/handle/100/15995
 
Language en