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Synthesis and Structure-Property Relationship of Star Dyades and Triades as Novel, Filled Liquid Crystals

作为新型填充液晶的星形二元组和三元组的合成及其结构-性能关系

基本信息

批准号：
317672849
负责人：
Professor Dr. Matthias Lehmann
金额：
--
依托单位：
Institut für Organische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2016
资助国家：
德国
起止时间：
2015-12-31 至 2020-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/317672849?language=en
关键词：
Synthesis Structure Property Relationship Star

项目摘要

Shape-persistent three-armed oligo(phenylenevinylene) star mesogens form columnar liquid crystalline mesophases despite the large free volume between their linear conjugated arms. The interconnection of the oligo(phenylenevinylene) arms of these star mesogens, which are donors, with fullerene building blocks via flexible spacers results in donor-acceptor dyads. Here the void is occupied by covalently bound fullerene guest molecules. The self-assembly of these molecules leads to novel filled columnar mesophases with nanosegregated donor-acceptor structures. The structural control is achieved by variation of the spacer length, the connection position, the length of the conjugated scaffold and the peripheral flexible chains. Clearing temperatures below 200 °C are realized by introduction of oligo(ethyleneoxy)- or branched chains. Star triades, based on Porphyrin and Phthalocyanine cores, to which fullerene containing stilbenoid arms are attached, are an extension of this concept. The materials structures are investigated by X-ray scattering techniques, UV-Vis- and fluorescence spectroscopy in solution and liquid crystal state. The results allow the set-up of models with the program package Materials Studio and lead to the in-depth knowledge of the structure-property relationships. The dense packing of donor and acceptor chromophores in a columnar structure should allow a fast charge transport to the electrodes in a device, if a homeotropic alignment can be achieved. The materials systems are therefore of special interest with respect to their photovoltaic properties. Charge separation and transport will be optimized not only by the tailor-made donor-acceptor mesogens but also by the preparation of mixtures between star triades with four ´bound fullerene guests, stars without fullerenes and suitable, functionalized fullerenes. The introduction of oligo(ethyleneoxy) chains are promising to promote charge separation owing to the increase of the materials dielectric constant. The liquid crystal state will be used for the correct alignment of the columns in thin solid films. The photovoltaic liquid crystal cells will be fabricated subsequently and their photovoltaic properties will be studied in collaboration with Prof. Grelet (Bordeaux).

形状持久的三臂低聚（亚苯基亚乙烯基）星星介晶形成柱状液晶中间相，尽管它们的线性共轭臂之间的大的自由体积。这些星星介晶的低聚（亚苯基亚乙烯基）臂（它们是供体）通过柔性间隔物与富勒烯结构单元的互连导致供体-受体二联体。这里的空隙被共价键合的富勒烯客体分子占据。这些分子的自组装导致新的填充的柱状中间相与nanosegliferated供体-受体结构。通过改变间隔区长度、连接位置、共轭支架的长度和外围柔性链来实现结构控制。通过引入低聚（乙烯氧基）或支链实现低于200 ° C的清除温度。星星三联体，基于卟啉和酞菁核，其上附着含有芪类臂的富勒烯，是这一概念的延伸。用X射线散射、紫外-可见光谱和荧光光谱研究了材料在溶液和液晶态的结构。结果允许与程序包材料工作室的模型的设置，并导致深入的结构-性能关系的知识。如果可以实现垂面配向，则在柱状结构中供体和受体发色团的密集堆积应允许快速电荷传输到装置中的电极。因此，该材料系统在其光伏特性方面具有特殊的意义。电荷分离和传输不仅可以通过定制的供体-受体介晶，而且可以通过制备具有四个结合富勒烯客体的星星三元组、没有富勒烯的星星和合适的官能化富勒烯之间的混合物来优化。低聚（乙烯氧基）链的引入是有希望的，以促进电荷分离，由于材料的介电常数的增加。液晶状态将用于薄固体膜中的列的正确对准。随后将制造光伏液晶电池，并与Grelet教授（波尔多）合作研究其光伏特性。