Alignment of palladium complexes into columnar liquid crystals driven by peripheral triphenylene substituents.
Alignment of palladium complexes into columnar liquid crystals driven by peripheral triphenylene substituents.
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DOI：
10.1021/ic402886t
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发表时间：
2014-03
影响因子：
4.6
通讯作者：
Emiliano Tritto;R. Chico;G. Sanz-Enguita;C. Folcia;J. Ortega;S. Coco;P. Espinet
中科院分区：
文献类型：
--
作者：
Emiliano Tritto;R. Chico;G. Sanz-Enguita;C. Folcia;J. Ortega;S. Coco;P. Espinet
合成了一种新的三苯基亚胺(μ-X)2[Pd2Im2](X=CH3COO(-)，Cl(-)，Br2(-))，(μ-Cl)(μ-SCnH2n+1)[Pd2Im2](n=6，12)，[PdIM(Acac)][PdIMCl(CNC6H4OC12H25)]，[PdImCl(CNC6H3(OC12H25)2)]和[PdImCl(CNC6H2(OC12H25)3)]。游离亚胺配体不是液晶，但大多数邻位金属双核钯配合物和单核三烷氧基苯基异氰酸酯衍生物在接近环境温度时都显示出柱状中间相。对于二聚络合物，得到的中间相总是柱状矩形(Colr)，具有一种不常见的结构：二聚三苯-钯络合物-三苯分子形成了由两列堆积的三苯基连接到由两个邻苯二聚体部分堆积而成的中心柱组成的三柱堆积。对于三烷氧基苯基异氰酸酯衍生物，发现了一种相关的类聚合物柱排列，三苯的堆积与两个邻苯二聚体的堆积交替进行。中间相结构为柱状倾斜(Colob)。在二氯甲烷溶液中，游离亚胺和所有钯配合物在室温下都显示出与三苯基核相关的荧光。
A new triphenylene-imine (ImH) and its ortho-palladated complexes (μ-X)2[Pd2Im2] (X = CH3COO(-), Cl(-), Br(-)), (μ-Cl)(μ-SCnH2n+1)[Pd2Im2] (n = 6, 12), [PdIm(acac)] [PdIm Cl(CNC6H4OC12H25)], [PdImCl(CNC6H3(OC12H25)2)], and [PdImCl(CNC6H2(OC12H25)3)] have been prepared. The free imine ligand is not a liquid crystal, but most ortho-metalated dinuclear palladium complexes and the mononuclear trialkoxyphenyl isocyanide derivative display columnar mesophases at temperatures close to ambient. For the dimeric complexes the mesophase obtained is always columnar rectangular (Colr), with an uncommon structure: the dimeric triphenylene-Pd complex-triphenylene molecules give rise to a triple-column stacking consisting of two columns of stacked triphenylene groups connected to a central column formed by stacking of two ortho-palladated dimeric moieties. For the trialkoxyphenyl isocyanide derivative a related polymer-like arrangement of columns alternating stacking of triphenylenes with stacking of two ortho-palladated dimeric moieties is found. The mesophase structure is columnar oblique (Colob). The free imine and all palladium complexes exhibit fluorescence at room temperature in dichloromethane solution, associated with the triphenylene core.