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Current Inorganic Chemistry
ISSN (Print): 1877-9441
ISSN (Online): 1877-945X
VOLUME: 3
ISSUE: 3
DOI: 10.2174/1877944103666140110225547      Price:  $58









Analysis of the Magnetic Exchange Interaction in Halide-Bridged Cu(II) Binuclear Complexes: Deciphering the Paths

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Author(s): Boris Le Guennic and Nicolas Ferré
Pages 235-241 (7)
Abstract:
Following a recently reported synthesis of linearly halide-bridged Cu(II) complexes [Inorg. Chem. 2012, 51, 7966-7968] characterized by strong antiferromagnetic exchange couplings (J), we applied Difference Dedicated Configuration Interaction (DDCI) and Broken-Symmetry Density Functional Theory (BS-DFT) approaches in order to analyze theoretically the trend observed, in which the decreasing electronegativity of the central halide induces an exacerbed magnetic coupling. The importance of the magnetic orbitals in DDCI calculations is acknowledged. The use of reduced molecular models is shown to lead to significant differences in J, in the case of chloride and bromide bridges. Finally, the BS-DFT decomposition of J in its main physical contributions confirms the importance of the kinetic exchange mediated by the halide bridge, but also points towards an increasing core polarization contribution when going from fluoride to bromide.
Keywords:
Broken-Symmetry DFT, Difference Dedicated CI, Magnetic exchange coupling.
Affiliation:
Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, 13397 Marseille Cedex 20, France.