[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

二茂金属M'(C~5H~5)~2]^1^+的盐与(NBu~4)~nM(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]~nNi(dmit)~2]和Co(C~5H~5)~2]~nPd(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。

Synthesis and characterization of [Co(C~5H~5)~2]~n.[M(dmit)~2](M=Ni, Pd;n=0,1,2)

The reaction of metallocene cations M'(C5H5)2]+ with (NBu4)n M(dmit)2] (I; 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 salts Co(C5H5)2]nNi(dmit)2] and Co(C5H5)2]nPd(dmit)2] with only weak charge-transfer properties were obtained. The charge transfer states of these complexes were discussed based on ESCA, Raman spectra and cyclic voltammetric experiments Ni(dmit)2 and Pd(dmit)2 exhibit a semiconductive conductivity temperature dependence, although their elec. conductivity at room temperature is 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.