title: Magnetostructural correlations in Cu(II)-NC-W(V) linkage: the case of [Cu(II)(diimine)]2+-[W(V)(CN)8]3- 0D assemblies.
abstract: We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [Cu(II)(phen)(3)](2){[Cu(II)(phen)(2)](2)[W(V)(CN)(8)](2)}(ClO(4))(2) x 10 H(2)O (phen = 1,10-phenanthroline) (1) and {[Cu(II)(bpy)(2)](2)[W(V)(CN)(8)]} {[Cu(II)(bpy)(2)][W(V)(CN)(8)]} x 4 H(2)O (bpy = 2,2'-bipyridyl) (2). Compound 1 consists of cyano-bridged [Cu(II)(2)W(V)(2)](2-) molecular rectangles and isolated [Cu(II)(phen)(3)](2+) complexes. The molecular structure of 2 reveals cyano-bridged trinuclear [Cu(II)(2)W(V)](+) and dinuclear [Cu(II)W(V)](-) ions. Magnetic interactions in 1 are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic Cu(II)-NC-W(V) units (J(1) = +39(4) cm(-1)) interacting antiferromagnetically (J(2) = -1.6(4) cm(-1)). The analysis of the magnetic response of 2 reveals ferromagnetic interaction within the [Cu(II)-NC-W(V)-CN-Cu(II)](+) and [Cu(II)-NC-W(V)](-) isolated units, characterized by J = +35(7) cm(-1) and antiferromagnetic coupling between them (4J' = -0.30(8) cm(-1)). The discussion of the magnetic behavior and the correlation of the J(CuW) parameters with the geometry of cyano bridges at copper(II) centers of 1 and 2 is based on the DFT calculations, which yield J(av) = +13.2 cm(-1) for 1 and J = +31 cm(-1) for 2. The domination of the ferromagnetic Cu(II)-NC-W(V) interaction in 1 and 2 originates from the mutual orthogonality of natural magnetic orbitals in the case of coordination of cyano bridges at the equatorial sites of Cu(II) moieties.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland. korzenia@chemia.uj.edu.pl
authors.forename: Tomasz
authors.initials: T
authors.lastname: Korzeniak
authors.forename: Cédric
authors.initials: C
authors.lastname: Desplanches
authors.forename: Robert
authors.initials: R
authors.lastname: Podgajny
authors.forename: Carlos
authors.initials: C
authors.lastname: Giménez-Saiz
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Stadnicka
authors.forename: Michał
authors.initials: M
authors.lastname: Rams
authors.forename: Barbara
authors.initials: B
authors.lastname: Sieklucka