Ni(III) Mott-Hubbard-like State Containing High-Spin Ni(II) in a Semiconductive Bromide-Bridged Ni-Chain Compound.

Halogen-bridged linear chain metal complexes (MX-Chains) are fascinating compounds that have a quasi-one-dimensional (1D) electronic system. In this study, we synthesized the first Ni-based MX-Chain compound having hydroxy groups, i.e., [Ni(dabdOH)Br]Br·[Ni(dabdOH)Br]·(2-PrOH)·(MeOH) (·solvent, = ∼0.6, dabdOH = (2,3)-2,3-diaminobutane-1,4-diol). Single-crystal X-ray diffraction revealed that the MX-Chains in ·solvent formed sheets and single-chain structures in the superlattice. It suggested an MH-like state, whereas the polarized reflection and Raman spectra suggested a CDW-like state. Magnetic and electron spin resonance measurements revealed that both high-spin Ni(II) (∼15%) and low-spin Ni(III) (∼85%) sites are present in the chain structures, i.e., the metal sites show mixed valency. Therefore, we concluded that ·solvent adopts an intermediate state between the MH and CDW states. Moreover, a single crystal of ·solvent exhibited semiconductive characteristics along the chain direction. This finding represents a new structural and electronic state of 1D electronic systems as well as MX-Chains.