Triggering the Sign of Magnetic Exchange Coupling in a Dinuclear Copper(II) Complex by Solvent Molecule Coordination. Issue 28 (5th August 2013)

• Record Type: Journal Article
• Authors: Shcherbakov, Igor N.; Levchenkov, Sergey I.; Tupolova, Yulia P.; Popov, Leonid D.; Vlasenko, Valery G.; Zubavichus, Yan V.; Lukov, Vladimir V.; Kogan, Victor A.
• Is Part Of: European journal of inorganic chemistry. Issue 28(2013)
• Page Start: 5033
• Page End: 5043
• Publication Date: 2013-08-05
• Subjects: Copper -- Magnetic properties -- Exchange interactions -- Density functional calculations -- Broken symmetry; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300670
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The magnetic properties of a dinuclear copper(II) complex of the Schiff base ligand bis( N, N′ ‐3‐formylsalicylidene)‐1, 3‐diaminopropan‐2‐ol (H3 L) with an exogenous acetate bridging group, [Cu2 L(CH3 COO)] (2 ), and the product of its crystallization from dimethyl sulfoxide (DMSO) solution, [Cu2 L(CH3 COO)(DMSO)] (3 ), are studied experimentally and theoretically. The coordination of a DMSO molecule triggers exchange coupling from antiferromagnetic in2 (2 J = –94.8 cm –1 ) to ferromagnetic in3 (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 of2 and3 is explained by a different conformation of the dinuclear unit, which is "symmetric" in2 and roof‐shaped in3 . The role of the DMSO molecule in exchange‐coupling sign inversion is limited to the stabilisation of the roof‐shaped conformation of the complex. Abstract : We report the first example of triggering of the sign of magnetic coupling in a dinuclear copper(II) complex by dimethyl sulfoxide (DMSO) solvation.