Electron Microscopy and Magnetic Properties of Tetra(n-butyl) ammonium salts of $[Ni(dmbit)_2]^1- (dmbit^2-:C_7H_2S_5$:2-thiobenzo[d]-1,3-dithiole-5,6-dithiolate;$dmbbip^{2-}:C_{12}H_{16}S_4$:1,2-bis(isopropylthio)benzene-4,5-dithiolat

• Published in: Bulletin of the Korean Chemical Society 1996, Vol.17 (1), p.46-50
• Main Authors: 노동연, 강미정, 이하진, 김종현, 최진호, No, Dong Yeon, Gang, Mi Jeong, Lee, Ha Jin, Kim, Jong Hyeon, Choe, Jin Ho
• Format: Article
• Language: Korean
• ISSN: 0253-2964; 1229-5949

Monoanionic nickel(Ⅲ) complexes, [Ni(dmbit)2]1- and [Ni(dmbbip)2]1- where dmbit2- and dmbbip2- denote 2-thiobenzo[d]-1,3-dithiole-5,6-dithiolate and 1,2-bis(isopropylthio)benzen-4,5-dithiolate, respectively, have been synthesized by the iodine oxidation of dianionic complexes. In the scanning electron microscopic(SEM) images, these complexes show the well-grown two-dimensional layered structures which are clearly comparable to the dianionic ones with three-dimensional structures. Magnetic susceptibilities of nickel(Ⅲ)complexes are fitted well with the two-dimensional Heisenberg antiferromagnet model of S=1/2 system resulting in the spin-exchange parameters (|J|/k) of 11.4 K and 0.45 K, respectively. The weaker magnetic interaction in [Ni(dmbbip)2]1- is resulted from the bulky isopropyl groups on the periphery of dmbbip ligand. EPR measurements for [Ni(dmbit)2]1- give the signal with axial symmetry and the anisotropic g-values for low-spin nickel(Ⅲ) (g//=2.158, g =2.030,gav=2.074 at 300 K; g//=2.162, g =2.038, gav=2.080 at 77 K). It is therefore concluded that nickel(Ⅱ) is oxidized to nickel(Ⅲ), rather than dmbit2- and dmbbip2- ligands are, by the iodine oxidation. The paramagnetic Ni(Ⅲ) would be located in the axial symmetry(D4h) with the electronic configuration of (dxz2dyz2dz22dxy1dx2-y20).