[Co(C_5H_5)_2]_n[M(dmit)_2](M=Ni,Pd;n=0,1,2)型配合物的合成及表征

Synthesis and Characterization of [Co (C_5H_5)_2]n·[M (dmit)_2](M=Ni, Pd; n=0, 1, 2)

二茂金属[M′(C_5H_5)_2]^(1+)的盐与(NBu_4)_n[M(dmit)_2](M=Ni,Pd;n=1,2)反应,当M′=Fe,Ni;n=1时,分别得到了导电配合物[Ni(dmit)_2]和[Pd(dmit)_2];当M′=Co,n=1,2时,分别得到的是电荷几乎不转移的4个盐[Co(C_5H_5)_2]_n[Ni(dmit)_2]和[Co(C_5H_5)_2]_n[Pd(dmit)_2]。用ESCA、Raman谱及循环伏安图讨论了上述化合物形成时的电荷转移量。尽管[M(dmit)_2]的室温电导率相当大,但其电导率随温度的变化曲线表明它们属于半导体。EHCO能带计算给出[Ni(dmit)_2]的能隙0.112eV,与实测的电导活化能相当接近。

The reaction of metallocene cations [M'(C_5H_5)_2]^+ with (NBu_6), [M(dmit)_2] (M=Ni, Pd; n=1, 2) are reported. When M'=Fe, Ni; n=1 conducting complexes Ni. (dmit)_2 and Pd(dmit)_2 were obtained, and when M'=Co; n=1, 2 four no charge transfer salts [Co (C_5H_5)_2]_n[Ni(dmit)_2] and [Co(C_5H_5)_2]_n[Pd (dmit)_2] were obtained. The charge transfer states of these complexes were discussed based on ESCA, Raman spectra and cyclic voltammogram experiments. Ni (dmit)_2 and Pd(dmit)_2 exhibit a semiconductive conductivity temperature dependence, although their electric conductivity at room temperature are quite high. Tight binding band calculation gives the energy gap of Ni(dmit)_2 0.112 eV which is in accord with the measured activation energy.