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Magnetic Anisotropy of Mononuclear Ni-II Complexes: On the Importance of Structural Diversity and the Structural Distortions

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Title Magnetic Anisotropy of Mononuclear Ni-II Complexes: On the Importance of Structural Diversity and the Structural Distortions
 
Creator SINGH, SK
GUPTA, T
BADKUR, P
RAJARAMAN, G
 
Subject CASSCF calculations
magnetic anisotropy
nickel
magneto-structural correlations
zero-field splitting
SINGLE-MOLECULE MAGNETS
TRANSITION-METAL-COMPLEXES
DENSITY-FUNCTIONAL THEORY
ZERO-FIELD SPLITTINGS
HETEROLEPTIC NICKEL(II) COMPLEXES
SPIN-HAMILTONIAN PARAMETERS
STATE PERTURBATION-THEORY
NI(II) COMPLEXES
COORDINATION-COMPLEXES
LANTHANIDE COMPLEXES
 
Description Mononuclear Ni-II complexes are particularly attractive in the area of single-molecule magnets as the axial zero-field splitting (D) for the Ni-II complexes is in the range of -200 to +200cm(-1). Despite this advantage, very little is known on the origin of anisotropy across various coordination ligands, coordination numbers, and particularly what factors influence the D parameter in these complexes. To answer some of these questions, herein we have undertaken a detailed study of a series of mononuclear Ni-II complexes with ab initio calculations. Our results demonstrate that three prominent spin-conserved low-lying d-d transitions contribute significantly to the D value. Variation in the sign and the magnitude of D values are found to correlate to the specific structural distortions. Apart from the metal-ligand bond lengths, two different parameters, namely, and , which are correlated to the cis angles present in the coordination environment, are found to significantly influence the axial D values. Developed magneto-structural D correlations suggest that the D values can be enhanced significantly by fine tuning the structural distortion in the coordination environment. Calculations performed on a series of Ni-II models with coordination numbers two to six unfold an interesting observationthe D parameter increases significantly upon a reduction in coordination number compared with a reference octahedral coordination. Besides, if high symmetry is maintained, even larger coordination numbers yield large D values.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-12-28T12:43:13Z
2014-12-28T12:43:13Z
2014
 
Type Article
 
Identifier CHEMISTRY-A EUROPEAN JOURNAL, 20(33)10305-10313
0947-6539
1521-3765
http://dx.doi.org/10.1002/chem.201402694
http://dspace.library.iitb.ac.in/jspui/handle/100/16579
 
Language English