Ferromagnetic exchange coupling of vanadium(IV) dπ spins across pyrimidine rings:: Dinuclear complexes of oxovanadium(IV) bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionate) bridged by pyrimidine derivatives

Dinuclear oxovanadium(IV) complexes bridged by pyrimidine derivatives, L[VO(hfac)(2)](2) [L = pyrimidine (PM), 4-methylpyrimidine (MPM), 4,6-dimethylpyrimidine, 4-aminopyrimidine, and quinazoline; hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate], were synthesized and characterized. All of them showed intramolecular ferromagnetic interaction, and the magnetic susceptibilities were analyzed on the basis of the singlet-triplet model, giving 2J/k(B) = 2.2-5.5 K. PM[VO(hfac)(2)](2) crystallized in a monoclinic space group C2/c with a = 34.092(2), b = 6.9783(4), and e = 16.4940(9) Angstrom, beta = 109.104(1)degrees, V = 3707.8(4) Angstrom (3), and Z = 4 for C24H8F24N2O10V2, and MPM[VO(hfac)(2)](2) gave isomorphous crystals. A semiempirical calculation study based on the determined structure suggests the presence of d pi -p pi interaction between vanadium and pyrimidine nitrogen atoms. Ferromagnetic coupling is explained in terms of a spin-polarization mechanism across the pyrimidine bridge. The intermolecular ferromagnetic interaction of PM[VO(hfac)(2)](2) call be interpreted by the contact between the spin-polarized pyrimidine moiety and the oxovanadium oxygen atom in an adjacent molecule.