Preparation by electrocrystallisation has been carried out for the salts [Rb(anti-dchyl-18c6)]2[Ni(dmit)2] 1, [Rb(anti-dchyl-18c6)][Ni(dmit)2] 2, [Cs(anti-dchyl-18c6)]2[Ni(dmit)2] 3 and [Cs(anti-dchyl-18c6)1.5][Ni(dmit)2]64 (anti-dchyl-18c6 = cis-anti-cis-dicyclohexyl-18-crown-6, dmit = C3S5). Salts 1 and 3 involve the planar dianionic nickel complex sandwiched by two metalâcrown units. This leads to short Rb+ââ¯âNi and Rb+ââ¯âS interactions in 1 and the shortest recorded Cs+ââ¯âNi distance of 3.47 Ã
in 3, presumably stabilised by the four surrounding S atoms at 3.73â4.44 Ã
. DFT calculations on the dianionic salts 1 and 3 indicate an essentially electrostatic interaction between the [Ni(dmit)2]2â complex and the Rb+ or Cs+ ion and show frontier orbitals qualitatively similar to those previously derived from EHMO calculations on molecular conductors containing [Ni(dmit)2]. Salt 2 consists of non-stacked nickel complexes arranged in chains linked by Sââ¯âRb+ interactions through the terminal sulfurs with the Rb+ ion placed exactly within the plane of the crown oxygens. Magnetic susceptibility measurement indicated weak antiferromagnetic interactions. Salt 4 shows a 2-D sheet of nickel complexes stacked in a herringbone arrangement separated by layers of counter ions complexed by the crowns in a disordered manner with the anion â¶Â cation ratio of 6 â¶Â 1 uniquely high among [Ni(dmit)2]xâ salts. Salt 4 displays semiconductor behaviour with ÏRT = 10â2 S cmâ1.
通过电结晶法制备了 [Rb(anti-dchyl-18c6)]2[Ni(dmit)2] 1、[Rb(anti-dchyl-18c6)][Ni(dmit)2] 2、[Cs(anti-dchyl-18c6)]2[Ni(dmit)2] 3 和 [Cs(anti-dchyl-18c6)1.5][Ni(dmit)2]64(anti-dchyl-18c6 = cis-anti-cis-dicyclohexyl-18-crown-6, dmit =Â
C3S5)。盐 1 和盐 3 包含夹在两个
金属冠单元中的平面二离子
镍络合物。这导致 1 中的 Rb+ââ¯ââNi 和 Rb+ââ¯âS 相互作用较短,而 3 中记录的最短 Cs+ââ¯âNi 距离为 3.47 Ã,可能是由周围的四个 S 原子稳定在 3.73â4.44 Ã。对二离子盐 1 和 3 的 DFT 计算表明,[Ni(dmit)2]2â 复合物与 Rb+ 或 Cs+ 离子之间基本上存在静电作用,并显示出与之前通过对含有 [Ni(dmit)2] 的分子导体进行 EHMO 计算得出的前沿轨道性质相似的前沿轨道。盐 2 由非堆叠的
镍络合物组成,这些
镍络合物通过末端的
硫以 Sââ¯âRb+ 相互作用连接成链,Rb+ 离子正好位于冠氧原子的平面内。磁感应强度测量结果表明,它们之间存在微弱的反
铁磁相互作用。盐 4 显示了一个以人字形排列方式堆叠的二维片状
镍络合物,它被由冠氧根络合的反离子层以无序的方式隔开,其阴离子§¶Â阳离子比率为 6§¶Â 1,在[Ni(dmit)2]xâ 盐中是独一无二的高比率。盐 4 具有ÏRTÂ =Â 10â2 S cmâ1 的半导体特性。