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Triggering the Sign of Magnetic Exchange Coupling in a Dinuclear Copper(II) Complex by Solvent Molecule Coordination
Author(s) -
Shcherbakov Igor N.,
Levchenkov Sergey I.,
Tupolova Yulia P.,
Popov Leonid D.,
Vlasenko Valery G.,
Zubavichus Yan V.,
Lukov Vladimir V.,
Kogan Victor A.
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300670
Subject(s) - chemistry , crystallography , molecule , copper , antiferromagnetism , solvent , x ray absorption spectroscopy , bridging ligand , absorption spectroscopy , crystal structure , organic chemistry , physics , quantum mechanics , condensed matter physics
The magnetic properties of a dinuclear copper(II) complex of the Schiff base ligand bis( N , N′ ‐3‐formylsalicylidene)‐1,3‐diaminopropan‐2‐ol (H 3 L) with an exogenous acetate bridging group, [Cu 2 L(CH 3 COO)] ( 2 ), and the product of its crystallization from dimethyl sulfoxide (DMSO) solution, [Cu 2 L(CH 3 COO)(DMSO)] ( 3 ), are studied experimentally and theoretically. The coordination of a DMSO molecule triggers exchange coupling from antiferromagnetic in 2 (2 J = –94.8 cm –1 ) to ferromagnetic in 3 (2 J = +121 cm –1 ). A combination of experimental data [XRD, X‐ray absorption spectroscopy (XAS)] and the results of DFT calculations with a broken‐symmetry approach show that the different magnetic behaviour of 2 and 3 is explained by a different conformation of the dinuclear unit, which is “symmetric” in 2 and roof‐shaped in 3 . The role of the DMSO molecule in exchange‐coupling sign inversion is limited to the stabilisation of the roof‐shaped conformation of the complex.