Crossover from Antiferromagnetic to Ferromagnetic Exchange Coupling in a New Family of Bis-(μ-phenoxido)dicopper(II) Complexes: A Comprehensive Magneto-Structural Correlation by Experimental and Theoretical Study

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Details zur Publikation

Autorinnen und Autoren: Mondal D, Majee MC, Bhattacharya K, Long J, Larionova J, Khusniyarov M, Chaudhury M
Zeitschrift: ACS Omega
Jahr der Veröffentlichung: 2019
Band: 4
Heftnummer: 6
Seitenbereich: 10558-10570
ISSN: 2470-1343


Abstract

Five neutral bis(μ-phenoxido)dicopper(II) complexes, [Cu2(LMe,Me,Me)2] (1), [Cu2(LMe,Me,Et)2]·CH2Cl2 (2), [Cu2(Li-Pr,i-Pr,i-Pr)2]·2H2O (3), [Cu2(Lt-Bu,Me,i-Pr)2] (4), and [Cu2(Lt-Bu,t-Bu,i-Pr)2]·H2O (5) have been synthesized and characterized by single-crystal X-ray diffraction analyses, magnetic studies, and density functional theory (DFT) calculations, in which the ligands [H2LMe,Me,Me = N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-N′,N′-dimethylethylene-1,2-diamine, H2LMe,Me,Et = N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-N′,N′-dimethylethylene-1,2-diamine, H2Li-Pr,i-Pr,i-Pr = N,N-bis(2-hydroxy-3,5-diisopropylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine, H2Lt-Bu,Me,i-Pr = N,N-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine, and H2Lt-Bu,t-Bu,i-Pr = N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine] contain the same [O,N,N,O]-donor atoms combination but differ in substituents at phenol rings and at an amino nitrogen atom. The effect of these remote substituents on the nature of exchange coupling interactions (ferromagnetic vs antiferromagnetic) between the copper(II) ions has been investigated. The average Cu-O-Cu angle, Cu-O-Cu-O torsion angle, and Cu⋯Cu separation in 1-5 are varied systematically by these remote ligand substituents in the range 98.6-83.3°, 26.0-46.5°, and 2.982-2.633 Å, respectively. As a result, the intramolecular spin-spin coupling in these complexes are changing gradually from a strong antiferromagnetic (J = -395 cm-1, where Ĥ = -JŜ1Ŝ2) to a moderate ferromagnetic (J = +53.2 cm-1) regime. The crossover angle at which the magnetic interaction changes from antiferromagnetic to ferromagnetic (J = 0) is determined to be ca. 87° for this series of dicopper(II) complexes. DFT calculations support the experimentally determined crossover angle and disclose various magneto-structural correlations in the series 1-5.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Khusniyarov, Marat PD Dr.
Department Chemie und Pharmazie


Einrichtungen weiterer Autorinnen und Autoren

Indian Association for the Cultivation Of Science
University of Montpellier / Université Montpellier


Zitierweisen

APA:
Mondal, D., Majee, M.C., Bhattacharya, K., Long, J., Larionova, J., Khusniyarov, M., & Chaudhury, M. (2019). Crossover from Antiferromagnetic to Ferromagnetic Exchange Coupling in a New Family of Bis-(μ-phenoxido)dicopper(II) Complexes: A Comprehensive Magneto-Structural Correlation by Experimental and Theoretical Study. ACS Omega, 4(6), 10558-10570. https://dx.doi.org/10.1021/acsomega.8b03656

MLA:
Mondal, Dhrubajyoti, et al. "Crossover from Antiferromagnetic to Ferromagnetic Exchange Coupling in a New Family of Bis-(μ-phenoxido)dicopper(II) Complexes: A Comprehensive Magneto-Structural Correlation by Experimental and Theoretical Study." ACS Omega 4.6 (2019): 10558-10570.

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Zuletzt aktualisiert 2019-04-07 um 03:08