Discotic Liquid Crystals based on Tristriazolotriazines: Synthesis, Properties and the tangential-radial Isomerization

基于三三唑并三嗪的盘状液晶：合成、性质和切向径向异构化

• 批准号: 263531867
• 负责人: Professor Dr. Heiner Detert
• 金额: --
• 依托单位: Institut für Organische Chemie (aufgelöst)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/263531867?language=en
• 关键词: Discotic; Liquid; Crystals; based; Tristriazolotriazines

Two isomeric [1,3,4]tristriazolo[1,3,5]triazines with C3 symmetry and pi-conjugated substituents, either in a tangential or in a radial arrangement, are investigated. Thermal treatment of the `tangential`-isomer at elevated temperatures results in a stepwise rearrangement of the heterocyclic system. The annulation of the triazoles changes and the substituents are shifted from the original `tangential`- to a ´radial`-orientation. The thus formed ´radial`-tristriazolotriazine is a new heterocyclic core for discotic liquid crystals. Independent pathways for the synthesis of both isomers include cyclocondensation and oxidation of triazinylamides and -hydrazides.Optimisation of the isomerisation procedure is combined with kinetic and mechanistic studies. For this purpose, the first tristriazolotriazines with a non-symmetric core will be prepared. Combining donor- and acceptor substitution will discriminate the triazole-triazole bonds and shed light on the selectivity and sequence of the isomerisation steps. C3-symmetric cores with an asymmetric peripherie will be prepared. míxed lengths of the alkyl chains and mixed substitution pattern are used for a tuning of the thermal properties. Unprecedented tristriazolotriazines with styryl- and diaryl-1,3,4-oxadiazole as pi-segmente will be prepared: the diaryl-1,3,4-oxadiazole will result in strongly elektron deficient discs, usefuls as n-type semiconductors. Styryl-substitution opens the door to photochemistry: [2+2]-cycloadditions in solution can lead to cyclophanes, in the LC-Phase, photochemical cross-linking can stabilise the columns. Tristriazolotriazines are strongly emissive fluorophores with the ability to form broad thermotropic mesophases. The synthesis and rearrangement of tristriazolotriazines is acompanied by extensive characterisation of the optical, electrical and thermal properties of these materials, including experiments for the induction of helical chirality in the mesophase.

研究了两种具有C3对称性的异构体[1,3,4]三轮氮嗪，并且在切线或径向排列中进行了PI偶联的子函数。在升高温度下的“切向偶像体的热处理”导致杂环系统的逐步重排。三唑的一环会发生变化，并从原始的“切向”转移到了“放大”方向。如此形成的‘radial`-tristiazolotriazine是局部液晶的新杂环核心。合成这两种异构体的独立途径包括三唑胺和氢氮化物的环敏和氧化。异构化过程的优化与动力学和机械研究结合在一起。为此，将制备第一个具有非对称核心的tristristiazolotrazine。结合供体和受体取代将区分三唑 - 三唑键，并阐明异构化步骤的选择性和序列。将制备具有不对称外围的C3对称核。烷基链的míx长度和混合取代模式用于调整热性能。将准备具有苯乙烯和日记1,3,4-氧二唑作为Pi-Segmente的前所未有的tristriazololotrazine：Diaryl-1,3,4-氧化唑将导致强烈的Elektron防御盘，以N型Pe半管子的用途。 Styryl-subsubsitution为光化学打开了门：[2+2] - 溶液中的循环载体可以导致环光，在LC相，光化学交联可以稳定柱。 tristriazolotrazine是强烈的发射荧光团，具有形成宽嗜热中介液的能力。通过对这些材料的光学，电和热性质的广泛表征，包括诱导中间体中螺旋手性的实验，跨性别，电和热性能的广泛表征，对tristriazolotrazines的合成和重排具有促进。

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