Electronic Structure and Nature of the Ground State of the Mixed‐Valence Binuclear Tetra(μ‐1,8‐naphthyridine‐N,N′)‐bis(halogenonickel) Tetraphenylborate Complexes: Experimental and DFT Characterization

摘要: The ground state electronic structure of the mixed-valence systems [Ni(2)(napy)(4)X(2)](BPh(4)) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence magnetic susceptibility, and high-field EPR spectroscopy) theoretical (DFT) methods. zero-field splitting (zfs) S=3/2 spin is axial /D/ approximately 3 cm(-1). iodide derivative found to be isostructural previously reported bromide complex, but not isomorphous. compound crystallizes in monoclinic system, space group P2(1)/n, a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on characterize potential energy surface as a function nuclear displacements. molecules can thus classified Class III compounds computed delocalization parameter, B=3716, 3583, 3261 cm(-1) for Cl, I derivatives, respectively.