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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/12334
Title: Slow magnetic relaxation in dinuclear CoIIYIII Complexes
Authors: Acharya J.
Swain A.
Chakraborty A.
Kumar V.
Kumar P.
Gonzalez J.F.
Cador O.
Pointillart F.
Rajaraman G.
Chandrasekhar V.
Published in: Inorganic Chemistry
Abstract: Four new dinuclear complexes, [Co(μ-L)(μ-CCl3COO)Y(NO3)2]·2CHCl3·CH3CN·2H2O (1), [Co(μ-L)(μ-CH3COO)Y(NO3)2]·CH3CN (2), [Co(μ-L)(μ-PhCOO)Y(NO3)2]·3CH3CN·2H2O (3), and [Co(μ-L)(μ-tBuCOO)Y(NO3)2]·CHCl3·2H2O (4), having a CoIIYIII core, have been synthesized by employing a ferrocene based compartmental ligand which was synthesized by the reaction of diacetyl ferrocene with hydrazine hydrate followed by a condensation reaction with o-vanillin. A general synthetic protocol was employed to synthesize complexes 1-4, where the metallic core was kept the same with changing the bridging carboxylate groups. In all the complexes, the main structural motif is kept similar by only slightly varying the substitution on the bridging acetate groups. This variation has resulted in a small but subtle influence on the magnetic relaxation of all these four compounds. Ab initio CASSCF/NEVPT2 calculations were carried out to assess the effect of the different substitutions of the bridging ligands on the magnetic anisotropy parameters and on orbital arrangements. Ab initio calculations yield a very large positive D value, which is consistent with the geometry around the CoII ion and easy plane anisotropy (gxx, gyy > gzz), with the order of the calculated D in the range of 72.4 to 91.7 cm-1 being estimated in this set of complexes. To ascertain the sign of zero-field splitting in these complexes, EPR spectra were recorded, which support the sign of D values estimated from ab initio calculations. © 2019 American Chemical Society.
Citation: Inorganic Chemistry (2019), 58(16): 10725-10735
URI: https://doi.org/10.1021/acs.inorgchem.9b00864
http://repository.iitr.ac.in/handle/123456789/12334
Issue Date: 2019
Publisher: American Chemical Society
ISSN: 201669
Author Scopus IDs: 57193733965
57193695689
57194504049
57193734482
57212043583
57204243305
6603422410
14623291900
6602194731
7006003609
Author Affiliations: Acharya, J., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India
Swain, A., Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India
Chakraborty, A., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India, Tata Institute of Fundamental Research, Gopanpally, Hyderabad, 500107, India
Kumar, V., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India
Kumar, P., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India
Gonzalez, J.F., Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 263 Avenue du Général Leclerc, Rennes Cedex, 35042, France
Cador, O., Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 263 Avenue du Général Leclerc, Rennes Cedex, 35042, France
Pointillart, F., Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 263 Avenue du Général Leclerc, Rennes Cedex, 35042, France
Rajaraman, G., Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India
Chandrasekhar, V., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India, Tata Institute of Fundamental Research, Gopanpally, Hyderabad, 500107, India
Funding Details: We thank the Department of Science and Technology (DST), India; the CNRS, Université de Rennes 1, the European Commission through the ERC-CoG 725184 MULTIPROSMM (project no. 725184) for financial support, and also support for the Single Crystal CCD X-ray Diffractometer facility at IIT-Kanpur. V.C. is grateful to the DST for a J. C. Bose fellowship. J.A. thanks Department of Science and Technology (DST), India for INSPIRE Senior Research Fellowship. J.A. is also thankful to Mr. Arup Sarkar, IITB, for discussion and help. G.R. would like to thank SERB for funding (CRG/2018/000430) and the IITB multifrequency EPR facility for recording the EPR spectra.
Corresponding Author: Pointillart, F.; Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 263 Avenue du Général Leclerc, France; email: fabrice.pointillart@univ-rennes1.fr
Appears in Collections:Journal Publications [ME]

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