Patterning of Discotic Liquid Crystals with Tunable Molecular Orientation for Electronic Applications

The large‐area formation of functional micropatterns with liquid crystals is of great significance for diversified applications in interdisciplinary fields. Meanwhile, the control of molecular alignment in the patterns is fundamental and prerequisite for the adequate exploitation of their photoelectric properties. However, it would be extremely complicated and challenging for discotic liquid crystals (DLCs) to achieve the goal, because they are insensitive to external fields and surface chemistry. Herein, a simple method of patterning and aligning DLCs on flat substrates is disclosed through precise control of the formation and dewetting of the capillary liquid bridges, within which the DLC molecules are confined. Large‐area uniform alignment occurs spontaneously due to directional shearing force when the solvent is slowly evaporated and programmable patterns could be directly generated on desired substrates. Moreover, the in‐plane column direction of DLCs is tunable by slightly tailoring their chemical structures which changes their self‐assembly behaviors in liquid bridges. The patterned DLCs show molecular orientation–dependent charge transport properties and are promising for templating self‐assembly of other materials. The study provides a facile method for manipulation of the macroscopic patterns and microscopic molecular orientation which opens up new opportunities for electronic applications of DLCs.     

Ionic Discotic Liquid Crystals

Ionic discotic liquid crystals are salts of discotic liquid crystals that may display lyotropic and thermotropic mesomorphism. Columnar structures of π-π stacking ionic discotic liquid crystals function not only as anisotropic organic semiconductors, similar to their neutral analogues, but they may also efficiently conduct ions. This combination of electronic and ionic conduction is only one of several unique properties that these materials may display, but their systematic investigation has been limited because of their often complex synthesis, purification, and characterization. However, a comprehensive account of existing reports on ionic discotic liquid crystals is not straightforward, despite their relatively small number, because publications are scattered across different areas of research, such as liquid crystals, ionic liquids, and ionic self-assembly. This review intends to provide a concise but comprehensive overview of the published work on ionic discotic liquid crystals and related compounds and is expected to stimulate further exploration. Highlighted in this review is the mesomorphism of ionic discotic liquid crystals and its dependence on structural changes, which is also the focus of most reported studies. Particular attention was given to the dependence of mesomorphism on the location and types of the charged groups as these are parameters unique to these compounds. Also described are electronic, optical, and other properties of these materials if reported.     

六(十二烷基)六苯并蒄的简便合成

为了提高六(十二烷基)六苯并蒄的收率,设计了一条新合成路线。该方法首先以二苯乙炔为初始原料,经过环化三聚和碘代得到六(4-碘苯基)苯,该中间体在钯催化下与1-溴代十二烷发生Kumada交叉偶联,最后环化氧化脱氢制得目标产物。借助于1 HNMR和元素分析手段表明产物是目标化合物,并对该材料的光学性能、热学性能以及电化学性能进行了研究。该路线使目标物的总收率由27%提高到40.9%。与文献提供的方法相比,新法具有合成步骤少、纯化难度低、成本低廉等优点。     

A UV‐Responsive Multifunctional Photoelectric Device Based on Discotic Columnar Nanostructures and Molecular Motors

Orientation control of ordered materials would not only produce new physical phenomenon but also facilitate the development of fancy devices. Discotic liquid crystals (DLCs) form 1D charge transport pathway by self‐organizing into columnar nanostructures via π–π stacking. However, controlling the electrical properties in such nanostructures with some direct and instant way is a formidable task for their high viscosity and insensitivity to external stimuli. Herein, the arbitrary control over electrical conductivity of such columnar nanostructures is achieved with UV light by incorporating DLCs with molecular motors. Highly ordered DLC microstripe arrays are generated on desired substrate through a capillary bridge dewetting strategy. The conductivity of the microstripes could be continuously modulated by 365 nm light due to the influence of molecular motion under UV irradiation on the electron orbital overlap of columnar nanostructures. This is so because the disorder degree of the DLC molecules is associated with the intensity of UV light and the doping concentration of molecular motors. Moreover, the device shows memory effect and reversible conductivity change. The DLC microstripe arrays are very promising for the applications in UV detectors, memory devices, optical switches, and so on.     

苯并菲类盘状液晶的合成及应用

为了改善扭曲向列相(TN)型液晶显示的视角差的现象,合成了一种具有苯并菲结构的盘状液晶单体,并以该盘状液晶单体为材料制备了简易的光学补偿膜片。以4-氯丁醇乙酸酯、对羟基苯甲酸甲酯和邻苯二甲醚为原料,通过七步反应以较高收率合成了一种具有苯并菲结构的盘状液晶单体。通过核磁共振(NMR)和元素分析(EA)确认了分子结构的正确性;利用偏光显微镜(POM)、预倾角测试仪和示差扫描量热仪(DSC)等对其液晶参数进行测定,并以该苯并菲单体为材料通过基板处理、摩擦配向、涂布等过程制备了光学补偿膜片。实验表明,该苯并菲盘状液晶单体具有负的光学各向异性值(Δn=-0.060 8)、较宽的向列相温宽(54.6~166.4℃),所制得的简易光学补偿膜片具有一定的补偿效果(R_(th)=137nm)。该苯并菲类盘状液晶化合物可以作为光学补偿膜材料使用,且制备方法简单,原料易得,收率较高,易于实现大规模生产。