【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.更多还原

【Abstract】 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 I₂/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） nm, c=1 67535（9） nm, α=90 233（5）°, β=92 107（6）°, γ=104 654（6）°; V=0 78925（9） nm 3; 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 S...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 Ω -1·cm -1. Along the c direction the sheets of conductive [Ni（dmit）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.更多还原