分子导体(PyH)[Ni(dmit)_2]_2的合成、结构与导电性  

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

作　　者：许文[1] 方奇[1] 薛刚[1] 于文涛[1] 刘国群[1] 张德清[2] 徐伟[2] 徐翠英[2] 张金彪[2] 

机构地区：[1]山东大学晶体材料国家重点实验室,济南250100 [2]中国科学院化学研究所,北京100080

出　　处：《化学学报》2002年第12期2153-2158,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.2 0 172 0 34and 2 9672 0 2 3);中国科学院有机固体开放实验室资助项目

摘　　要：合成了一种新的导电分子晶体(PyH)[Ni(dmit)2 ]2 (Py =pyridine,dmit=(C3S5)2 -=4,5 dimercapto 1,3 dithiole 2 thione),用元素分析、红外光谱对其进行了表征,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 5 92 2 7(4)nm,b =0 82 2 79(6)nm,c=1 675 3 5 (9)nm,α =90 2 3 3 (5)°,β =92 10 7(5)°,γ =10 4 65 4(6)°;V =0 7892 5 (9)nm3,Z =1.(PyH)[Ni(dmit)2 ]2 晶体中,导电组元[Ni(dmit)2 ]-0 5沿b轴方向形成具有二聚体结构的柱状堆积,在(0 0 1)面形成以肩并肩分子间的S S强相互作用为特征的二维导电层,这种二维导电层上的室温电导率为 0 13Ω-1·cm-1,在c轴方向,(PyH)+与[Ni(dmit)2 ]-0 5之间除库仑作用外,还存在N—H S,C—H S氢键相互作用.单晶(0 0 1)面上变温电阻的测定结果表明,在 90K到室温的温度范围内,(PyH)[Ni (dmit)2 ]2 具有半导体导电行为,导电激活能为 0 15eV.A new molecular conductor ( PyH) [ Ni ( dmit)(2)](2) ( Py = pyridine, dmit = ( C3S5)(2-) = 4,5-dimercapto-1,3-dithiole-2-thione) has been prepared by oxidation with I-2/NaI and characterized by elemental analysis and IR spectrum. The single crystal structure was determined by four-circle X-ray diffraction method. Crystallographic parameters for (PyH) [Ni(dmit)(2)](2): triclinic system; P-1 space group; a = 0.59227 (4) nm, b =0.82279(6) mn, c = 1.67535(9) nm, alpha = 90.233(5)degrees, beta = 92.107(6)degrees, gamma = 104.654(6)degrees; V = 0. 78925 (9) nm; Z = 1. Both [Ni (dmit)(2)](-0.5) anion and PyH+ cation are almost planar. [Ni(dmit)(2)](-0.5) is stacked to form columns of dimerised pairs along the b-axis. Short and intense (SS)-S-... contacts in side-by-side style build a kind of two-dimensional network in the (001) plane. The conductivity at one direction on (001) plane at room temperature was measured to be 0.13 Omega(-1) (.) cm(-1). Along the c direction the sheets of conductive [Ni(dTnit)(2)](-0.5) are structurally modulated by hydrogen bonds between anions and cations. The resistivity-temperature curve in the temperature range of 90 - 290 K shows that the title compound behaves as a semiconductor with quite narrow energy gap.

关 键 词：分子导体 合成 结构 导电性 (PyH)[Ni(dmit)2]2 镍配合物 吡啶阳离子 

分 类 号：O75[理学—晶体学]