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以 s-三嗪环为中心核的多功能超分子树枝状大分子:液晶、荧光和光电导性能。

Multifunctional supramolecular dendrimers with an s-triazine ring as the central core: liquid crystalline, fluorescence and photoconductive properties.

作者信息

Bucoş Madalina, Sierra Teresa, Golemme Attilio, Termine Roberto, Barberá Joaquín, Giménez Raquel, Serrano José Luis, Romero Pilar, Marcos Mercedes

机构信息

Departamento de Química Orgánica, Facultad de Ciencias-Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza (Spain).

出版信息

Chemistry. 2014 Aug 4;20(32):10027-37. doi: 10.1002/chem.201402646. Epub 2014 Jun 17.

Abstract

Novel liquid crystal (LC) dendrimers have been synthesised by hydrogen bonding between an s-triazine as the central core and three peripheral dendrons derived from bis(hydroxymethyl)propionic acid. Symmetric acid dendrons bearing achiral promesogenic units have been synthesised to obtain 3:1 complexes with triazine that exhibit LC properties. Asymmetric dendrons that combine the achiral promesogenic unit and an active moiety derived from coumarin or pyrene structures have been synthesised in order to obtain dendrimers with photophysical and electrochemical properties. The formation of the complexes was confirmed by IR and NMR spectroscopy data. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffractometry. All complexes displayed mesogenic properties, which were smectic in the case of symmetric dendrons and their complexes and nematic in the case of asymmetric dendrons and their dendrimers. A supramolecular model for the lamellar mesophase, based mainly on X-ray diffraction studies, is proposed. The electrochemical behaviour of dendritic complexes was investigated by cyclic voltammetry. The UV/Vis absorption and emission properties of the compounds and the photoconductive properties of the dendrons and dendrimers were also investigated.

摘要

通过以三聚嗪为中心核与三个源自双(羟甲基)丙酸的外围树枝状分子之间的氢键作用,合成了新型液晶(LC)树枝状聚合物。已合成带有非手性前体致晶单元的对称酸树枝状分子,以获得具有液晶性质的与三嗪的3:1配合物。为了获得具有光物理和电化学性质的树枝状聚合物,已合成了结合非手性前体致晶单元和源自香豆素或芘结构的活性部分的不对称树枝状分子。通过红外光谱和核磁共振光谱数据证实了配合物的形成。通过差示扫描量热法、偏光光学显微镜和X射线衍射法研究了液晶性质。所有配合物均表现出介晶性质,对称树枝状分子及其配合物为近晶相,不对称树枝状分子及其树枝状聚合物为向列相。提出了主要基于X射线衍射研究的层状中间相的超分子模型。通过循环伏安法研究了树枝状配合物的电化学行为。还研究了化合物的紫外/可见吸收和发射性质以及树枝状分子和树枝状聚合物的光电导性质。

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