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
✍ Scribed by Alessandro Bencini; Elisabetta Berti; Andrea Caneschi; Dante Gatteschi; Elisa Giannasi; Ivana Invernizzi
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 286 KB
- Volume
- 8
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
The ground state electronic structure of the mixed-valence systems Ni(2)(napy)(4)X(2) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence of the magnetic susceptibility, and high-field EPR spectroscopy) and theoretical (DFT) methods. The zero-field splitting (zfs) ground S=3/2 spin state is axial with /D/ approximately 3 cm(-1). The iodide derivative was found to be isostructural with the previously reported bromide complex, but not isomorphous. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on the S=3/2 state to characterize the ground state potential energy surface as a function of the nuclear displacements. The molecules can thus be classified as Class III mixed-valence compounds with a computed delocalization parameter, B=3716, 3583, and 3261 cm(-1) for the Cl, Br, and I derivatives, respectively.