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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/23654
Title: Azide-Coordination in Homometallic Dinuclear Lanthanide(III) Complexes Containing Nonequivalent Lanthanide Metal Ions: Zero-Field SMM Behavior in the Dysprosium Analogue
Authors: Kumar P.
Biswas S.
Swain, Abinash Kumar
Acharya J.
Kumar V.
Kalita P.
Gonzalez J.F.
Cador O.
Pointillart F.
Rajaraman G.
Chandrasekhar V.
Published in: Inorganic Chemistry
Abstract: A series of homometallic dinuclear lanthanide complexes containing nonequivalent lanthanide metal centers [Ln2(LH2)(LH)(CH3OH)(N3)]·xMeOH·yH2O [1, Ln = DyIII, x = 0, y = 2; 2, Ln = TbIII, x = 1, y = 1] have been synthesized [LH4 = 6-((bis(2-hydroxyethyl)amino)-N′-(2-hydroxybenzylidene)picolinohydrazide] and characterized. The dinuclear assembly contains two different types of nine-coordinated lanthanide centers, because the nonequivalent binding of the azide co-ligand as well as the varying coordination of the deprotonated Schiff base ligand. Detailed magnetic studies have been performed on the complexes 1 and 2. Complex 1 and its diluted analogue (15%) are zero-field SMMs with effective energy barriers (Ueff) of magnetization reversal equal to 59(3) K and 66(3) K and relaxation times of τ0 = 10(4) × 10-6 s and 10(4) × 10-8 s, respectively. On the other hand, complex 2 shows a field-induced SMM behavior. Combined ab initio and density functional theory calculations were performed to explain the experimental findings and to unravel the nature of the magnetic anisotropy, exchange-coupled spectra, and magnetic exchange interactions between the two lanthanide centers. © 2021 American Chemical Society.
Citation: Inorganic Chemistry, 60(12): 8530-8545
URI: https://doi.org/10.1021/acs.inorgchem.1c00249
http://repository.iitr.ac.in/handle/123456789/23654
Issue Date: 2021
Publisher: American Chemical Society
Keywords: Calculations
Density functional theory
Dysprosium
Ligands
Magnetic anisotropy
Magnetization reversal
Metal ions
Effective energy
Exchange coupled
Lanthanide complex
Lanthanide metal ions
Magnetic exchange interactions
Magnetic studies
Metal centers
Schiff-base ligands
Synthesis (chemical)
ISSN: 201669
Author Scopus IDs: 57241594300
57202213070
57193695689
57193733965
57225857596
57192302207
57205346803
6603422410
14623291900
6602194731
7006003609
Author Affiliations: Kumar, P., Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur, 208016, India
Biswas, S., Department of Geo-Chemistry, Keshav Deva Malaviya Institute of Petroleum Exploration, Dehradun, 248915, India
Swain, A., Department of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India
Acharya, J., Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur, 208016, India
Kumar, V., Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur, 208016, India
Kalita, P., Tata Institute of Fundamental Research, Hyderabad, Gopanpally, 500107, India
Gonzalez, J.F., Université de Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, Rennes, F-35000, France
Cador, O., Université de Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, Rennes, F-35000, France
Pointillart, F., Université de Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, Rennes, F-35000, France
Rajaraman, G., Department of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India
Chandrasekhar, V., Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur, 208016, India, Tata Institute of Fundamental Research, Hyderabad, Gopanpally, 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. P.K. and A.S. thank the University Grants Commission (UGC), India for Senior Research Fellowships. G.R. acknowledges DST/SERB for funding (Nos. CRG/2018/000430, DST/SJF/CSA-03/2018-10, SB/SJF/2019-20/12). We sincerely thank Mr. Prakash Nayak, NISER, Bhubanswar, Odisha, India, for the PXRD measurements. 725184; European Commission, EC; Department of Science and Technology, Ministry of Science and Technology, India, डीएसटी; University Grants Commission, UGC; Science and Engineering Research Board, SERB: CRG/2018/000430, DST/SJF/CSA-03/2018-10, SB/SJF/2019-20/12; Centre National de la Recherche Scientifique, CNRS; Université de Rennes 1; National Institute of Science Education and Research, NISER
Appears in Collections:Journal Publications [ME]

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