分子导体(Py Me)[Ni(dmit)_2]_2的合成、结构与导电性  

Synthesis, Structure and Conductivity of Molecular Conductor (PyMe)[Ni(dmit)_2]_2

作　　者：许文[1] 方奇[1] 薛刚[1] 于文涛[1] 刘国群[1] 雷虹[2] 

机构地区：[1]山东大学晶体材料国家重点实验室 [2]山东大学信息科学与工程学院,济南250100

出　　处：《化学学报》2004年第6期587-592,共6页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.2 0 1 72 0 34)资助项目

摘　　要：合成了一种新的导电分子晶体 (PyMe) [Ni(dmit) 2 ] 2 (Py =pyridine ,dmit =(C3 S5) 2 -=4,5 dimercapto 1,3 dithiole 2 thio nato) ,并用四圆X射线衍射方法确定了结构 ,该晶体属于三斜晶系 ,P 1空间群 ;晶胞参数为 :a =0 7483 7( 9)nm ,b =1 15 479( 16)nm ,c =1 9775 ( 3 )nm ,α =99 2 68( 12 )° ,β =99 14 0 ( 10 )° ,γ =99 673 ( 11)° ;V =1 63 2 0 ( 4 )nm3 ,Dc=2 0 2 9g/cm3 ,Z =2 .导电组元 [Ni(dmit) 2 ] 0 .5-沿 [-110 ]方向堆积成柱 (column) ,柱与柱之间进一步借助于大量的S…S分子间相互作用形成二维导电层 ,测得在 ( 0 0 1)面上的室温电导率为 10 -1～ 10 -4Ω-1·cm-1.用结构参数和分子间重叠积分相结合的方法 ,分析了导电性与结构的关系 .A new molecular conductor (PyMe)[Ni(dmit) 2] 2 (Py=pyridine, dmit=(C 3S 5) 2-=4,5-dimercapto-1,3-dithiole-2-thionato) has been synthesized and its structure determined by four-circle X-ray diffraction analysis. Crystallographic parameters for (PyMe)[Ni(dmit) 2] 2: triclinic system, P-1 space group; a=0.74837(9) nm, b=1.15479(16) nm, c=1.9775(3) nm, α=99.268(12)°, β=99.140(10)°, γ=99.673(11)°; V=1.6320(4) nm 3, D c=2.029 g/cm 3, Z=2. Structure analysis reveals that four-fold [Ni^(dmit) 2] 0.5- units stack to form columns along [-110] direction, and these columns further form 2-D conducting sheet by S…S intermolecular contacts. The conductivity on (001) plane is measured to be 10 -1～10 -4 Ω -1·cm -1. The relationship between conductivity and structure was discussed based on the structure parameters and intermolecular orbital overlap.

关 键 词：分子导体 (PyMe)[Ni(dmit)2]2 合成 结构 导电性 

分 类 号：O614[理学—无机化学]