Three molecular metals containing bis(maleonitriledithiolate)nickel(III) anion and 2-substituted benzyl triphenylphosphonium: Syntheses, crystal structures and magnetic properties

作者：Chen Wei Qiang; Li Yi Yuan; Ye Hui Qing; Zhang Zheng; Cai Hua Tang; Yu Jia Yu; Zhou Jia Rong^*; Yang Le Min; Ni Chun Lin

来源：Synthetic Metals, 2014, 193: 23-30.

DOI：10.1016/j.synthmet.2014.03.015

• Bis(maleonitriledithiolate)nickel(III)
• 2-Substituted benzyl
• triphenylphosphonium
• Crystal structure
• Magnetic properties

Three new molecular metals, [2RBzTPP][Ni(mnt)(2)] (mnt(2-) = maleonitriledithiolate; [2RBzTPP](+) = 1-(2'-R-benzyl)triphenylphosphonium, R = F(1), Br(2), NO2(3)) have been synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The single-crystal structure analysis indicates that I crystallizes in the triclinic space group P-1, while both 2 and 3 crystallizes in the monoclinic space group P2(1)/n. The Ni(III) ions of 1, 2, and 3 form a 1D non-uniform magnetic chain within a [Ni(mnt)(2)](-) anions column through Ni center dot center dot center dot Ni, Ni center dot center dot center dot S or S center dot center dot center dot S interactions. The effect of weak intramolecular interactions such as C-H center dot center dot center dot N, C-H center dot center dot center dot F, C-H center dot center dot center dot Br, C-H center dot center dot center dot pi or C-H center dot center dot center dot O hydrogen bonds in these molecular solids 1, 2 or 3 generate a 3D network structure. Magnetic measurements have shown that 1 exhibits a characteristic of spin-gap (Delta/k(b) = 249.5 K) around 128 Kappa, while 2 and 3 showed a very strong antiferromagnetic coupling feature with J = -875.6 and -820.3 cm(-1) when the temperature is lowered.

• 单位
  华南农业大学