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Observation of Ferromagnetic Exchange, Spin Crossover, Reductively Induced Oxidation, and Field-Induced Slow Magnetic Relaxation in Monomeric Cobalt Nitroxides

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Title Observation of Ferromagnetic Exchange, Spin Crossover, Reductively Induced Oxidation, and Field-Induced Slow Magnetic Relaxation in Monomeric Cobalt Nitroxides
 
Creator GASS, IA
TEWARY, S
NAFADY, A
CHILTON, NF
GARTSHORE, CJ
ASADI, M
LUPTON, DW
MOUBARAKI, B
BOND, AM
BOAS, JF
GUO, SX
RAJARAMAN, G
MURRAY, KS
 
Subject TRANSITION-METAL-COMPLEXES
NEUTRON-SCATTERING SPECTRA
SINGLE-MOLECULE MAGNETS
GAUSSIAN-BASIS SETS
ELECTRON DELOCALIZATION
BIS(NITROXYL) ADDUCTS
EXCITED-STATES
ENERGY-LEVELS
CHAIN MAGNET
ATOMS LI
 
Description The reaction of [Co-II(NO3)(2)]center dot 6H(2)O with the nitroxide radical, 4-dimethyl-2,2-di(2-pyridyl) oxazolidine-N-oxide (L-center dot), produces the mononuclear transition-metal complex [Co-II(L-center dot)(2)](NO3)(2) (1), which has been investigated using temperature-dependent magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, electrochemistry, density functional theory (DFT) calculations, and variable-temperature X-ray structure analysis. Magnetic susceptibility measurements and X-ray diffraction (XRD) 'analysis reveal a central low-spin octahedral Co2+ ion with both ligands in the neutral radical form (L-center dot) forming a linear L-center dot center dot center dot center dot Co(II)center dot center dot center dot L-center dot arrangement. This shows a host of interesting magnetic properties including strong cobalt-radical and radical-radical intramolecular ferromagnetic interactions stabilizing a S = 3/2 ground state, a thermally induced spin crossover transition above 200 K and field-induced slow magnetic relaxation. This is supported by variable-temperature EPR spectra, which suggest that 1 has a positive D value and nonzero E values, suggesting the possibility of a field-induced transverse anisotropy barrier. DFT calculations support the parallel alignment of the two radical pi*No orbitals with a small orbital overlap leading to radical-radical ferromagnetic interactions while the cobalt-radical interaction is computed to be strong and ferromagnetic. In the high-spin (HS) case, the DFT calculations predict a weak antiferrornagnetic cobalt-radical interaction, whereas the radical-radical interaction is computed to be large and ferromagnetic. The monocationic complex [Co-III(L-)(2)](BPh4) (2) is formed by a rare, reductively induced oxidation of the Co center and has been fully characterized by X-ray structure analysis and magnetic measurements revealing a diamagnetic ground state. Electrochemical studies on 1 and 2 revealed common Co-redox intermediates and the proposed mechanism is compared and contrasted with that of the Fe analogues.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-16T13:49:10Z
2014-10-16T13:49:10Z
2013
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 52(13)7557-7572
http://dx.doi.org/10.1021/ic400565h
http://dspace.library.iitb.ac.in/jspui/handle/100/15707
 
Language en