BIBLIOS

Document type
Journal articles

Document subtype
Full paper

Title
Cis–Trans Isomeric and Polymorphic Effects on the Magnetic Properties of Water-Bridged Copper Coordination Chains

Participants in the publication
Bojan Kozlev?ar (Author)
Nives Kitanovski (Author)
Zvonko Jagli?i? (Author)
Nuno A. G. Bandeira (Author)
BioISI
Vincent Robert (Author)
Boris Le Guennic (Author)
Patrick Gamez (Author)

Summary
The synthesis and magnetic characterization of vanillin-based Cu(II) mononuclear complexes of formula [Cu(van)2(H2O)2](H2O)x (van = vanillinate; x = 0, compound 1; x = 2, compounds 2 and 3) were performed. Despite the presence of very similar [Cu(van)2(H2O)2] moieties, the crystal structures exhibit distinct Cu···Cu contacts and display three different through-H-bond exchange-coupling pathways. As a result of the relative positions of the water molecules, the experimental (MAGSUS) exchange-coupling constants are dissimilar, i.e., J(1) = ?3.0 cm?1 (the data have been fitted to the Bleaney?Bowers equation considering a dimer; 2J = ?6.0 cm?1), J(2) = ?4.0 cm?1 (the data have been fitted to the Bonner?Fischer equation for a chain of monomeric copper(II) units), whereas compound 3 is paramagnetic. Subsequently, the theoretical density functional theory (DFT) and wave function theory-based (DDCI) calculations were carried out to better understand the role of the water molecule as a mediator of the magnetic coupling. The use of localized orbitals allows one to elucidate the role of the H-bonds in generating exchange interactions. Since the exchange-coupling constants are strongly dependent on the mechanisms selectively introduced, the role of the H-bond is demonstrated.


Where published
Inorganic Chemistry

Publication Identifiers
ISSN - 0020-1669

Publisher
American Chemical Society (ACS)



Document Identifiers
DOI - https://doi.org/10.1021/ic202568y
URL - http://dx.doi.org/10.1021/ic202568y

Rankings
SCIMAGO Q1 (2020) - 1.348 - Inorganic Chemistry
SCIMAGO Q1 (2020) - 1.348 - Physical and Theoretical Chemistry
Web Of Science Q1 (2020) - 5.165 - CHEMISTRY, INORGANIC & NUCLEAR - SCIE
SCIMAGO Q1 (2020) - 1.348 - Chemistry (miscellaneous)