含蒽刚柔三嵌段低聚物的合成及自组装

通过Sonogashira偶联等反应,合成了2种含蒽的三嵌段十字型化合物1和2;通过1H NMR和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF MS)对其结构进行了表征.利用差示扫描量热法(DSC)、偏光显微镜(POM)及小角X射线散射实验(SAXS)对2种化合物的本体自组装行为进行了研究.结果表明,在本体状态下,连接聚环氧乙烷(PEO)作为柔性链的化合物在液晶中间相自组装成倾斜柱状相和向列相,以烷基链为柔性链的化合物未形成液晶相,在固态相是层状结构.     

点击化学合成盘-棒-盘状液晶三聚体

本文设计并合成了一系列盘-棒-盘状液晶三聚体.此类三聚体由两个相同的苯并菲盘状介晶基元和一个联苯棒状介晶基元通过CuI-NEt3体系催化端基炔和端基叠氮化合物的点击反应连接形成.该三聚体结构通过核磁、红外和高分辨质谱表征;介晶性通过偏光显微镜(POM)、差示扫描量热法(DSC)和X射线衍射(XRD)进行了研究.结果显示:此类液晶三聚体均为室温液晶,呈现四方柱状相(Colr).连接3个介晶基元的柔性间隔基的长度对化合物的相转变温度具有明显影响.     

刚柔三嵌段共聚物的柱状结构构筑

合成了以酯键和醚键相连的苯和联苯作为刚棒B嵌段,以聚合度为7,12和17的聚环氧乙烷为A嵌段及辛基或十六烷基为C嵌段的ABC型三嵌段线团-刚棒-线团分子.通过核磁共振氢谱和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF MS)对其结构进行了表征,利用偏光显微镜(POM)、示差扫描量热法(DSC)和小角X射线散射实验(SAXS)对其本体状态下的自组装行为进行了研究.结果表明,聚环氧乙烷聚合度为7、烷基链分别为辛基和十六烷基的化合物1a和2a在固相和液晶态分别自组装成倾斜柱状结构和矩形柱状结构,而具有长聚环氧乙烷链的化合物2b、2c和1c在固相都自组装成倾斜柱状结构.发现聚环氧乙烷链和烷基链的长度显著地影响线团-刚棒-线团分子体系的自组装行为.通过改变线团-刚棒-线团分子体系中柔性链长度的策略,可以精确地调控刚柔三嵌段共聚物的聚集体结构.     

氢键稳定的苯并菲盘状液晶的合成及介晶性

盘状液晶分子能自组装成高度有序的六方柱状介晶相. 其各向异性的载流子高速迁移率使其成为较理想的有机光电子材料. 采用分子间氢键锚定柱状相, 获得介晶相温度范围宽、有序度高的苯并菲盘状液晶是本研究的目的. 本文通过分子设计, 合成了3个系列, 共18个有两种不同软链的苯并菲盘状液晶化合物C₁₈H₆(OR)₅(OCH₂COOEt), C₁₈H₆(OR)₅(OCH₂COOBu)和C₁₈H₆(OR)₅(OCH₂CONHBu), 其中R＝C_nH_2n＋1, n＝4～9. 化合物的纯度和结构通过¹H NMR和元素分析确证. 化合物热稳定性通过热重分析(TGA)测定, 并显示出较高的热稳定性. 通过偏光显微镜(POM)和差示扫描量热法(DSC)对这些化合物的热致液晶性进行了研究. 结果显示对于分子中含有酰胺基的苯并菲液晶化合物C₁₈H₆(OR)₅(OCH₂CONHBu), 与具有同样软链长度的分子中不含酰胺键的化合物系列C₁₈H₆(OR)₅(OCH₂COOBu)相比较, 前者由于柱内分子间氢键的形成, 具有更高的熔点和清亮点.     

不对称苯并菲盘状液晶的合成及取代基对介晶性的影响

合成了一系列新型含间位二硝基苯甲酸酯不对称苯并菲盘状液晶化合物2-(3,5-二硝基苯甲酰氧基)-3,6,7,10,11-五烷氧基苯并菲(3a～3f). 通过偏光显微镜(POM)和差示扫描量热计(DSC)对其介晶性进行了研究. 结果显示: 此类化合物有高的清亮点, 稳定的六方柱状相以及较宽的介晶相范围, 且随着软链碳原子数的增加, 化合物的熔点和清亮点均出现下降趋势, 但六方柱状相的有序性却没有发生很明显的变化. 同时通过与其它三类苯并菲盘状液晶2-苯甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(4a～4f), 2-二茂铁甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(5a～5f), 2,3,6,7,10,11-六烷氧基苯并菲(6a～6f)的对比研究, 探讨了酯基, 强吸电子基团, 以及取代官能团体积对介晶性的影响. 证实了苯并菲化合物中分子结构小的变化将引起介晶性大的改变.     

二乙炔桥连苯并菲盘状液晶二聚体的合成及其介晶性

通过桥链将2个盘状介晶基元相连,不仅可以稳定盘状液晶柱状相,还有利于玻璃态柱状相的形成,提高盘状液晶作为有机半导体材料的实用性．为此,通过铜盐催化的Eglinton偶联反应合成了8个二乙炔桥连的苯并菲盘状液晶二聚体化合物[C18H6（OCnH2n＋1）4（OMe）O2C—C8H16-C--C-]2,3（n）,（n=4-8）,[C18H6（OC6H13）5O2C—C8H16-C-C-]2,（6）和[C18H6（oc6H13）5O-（CH2）m-C-=C-]2,8（m）,（m=1,3）．差示扫描量热法（DSC）和热台偏光显微镜（POM）对其介晶性进行研究发现：（1）苯并菲周边柔链长度对液晶二聚体化合物的介品性有影响;（2）二聚体化合物3（n）和6具有玻璃态柱状相,并且所有苯并菲二聚体化合物在降温至-50℃均未出现结晶现象;（3）与二聚体3（6）相比,分子对称性较高的化合物6具有较稳定的柱状相,及较宽的介晶温度范围;（4）连接基、中心桥链的长度和刚性对苯并菲盘状液晶二聚体介晶性有重要影响．     

苯并菲盘状侧链液晶聚合物的大分子工程

盘状液晶聚合物兼具盘状液晶的光电性能和聚合物的柔韧性以及优异的成膜加工性能,有望发展成为新一代先进有机聚合物柔性光电功能材料.本文介绍苯并菲盘状侧链液晶聚合物的研究进展,主要结合我们研究组的工作,重点评述采用受控/活性自由基聚合方法可控合成这类侧链液晶聚合物以及对分子量效应和间隔基长度影响等基本问题的阐明.我们采用可逆加成-断裂链转移(RAFT)聚合第一次成功实现了分子量窄分布的苯并菲聚丙烯酸酯侧链盘状液晶聚合物的可控制备.首先提出盘单元局部簇集的分立短柱堆积(DCS)模型,合理解释了聚合度20左右出现的显著分子量效应,尤其揭示并提出了盘状侧链液晶聚合物的正耦合效应(PCE)理论,即短间隔基的较强耦合作用更有利于其有序柱状相的形成,与棒状侧链液晶聚合物经典的柔性长间隔基去耦合理论形成鲜明对照,补充了缺失的理论短板.基于这些原则,我们设计合成的丁氧基苯并菲聚丙烯酸酯侧链盘状液晶聚合物,经飞行时间谱(TOF)测试,表现出比文献报道值高1~2个数量级的载流子迁移率.进一步在手性客体分子掺杂诱导组装形成单手性螺旋结构聚合物复合物,以及拓扑受限环状聚合物和嵌段共聚物的受控制备等方面开展了比较系统的大分子工程实践.盘状侧链液晶聚合物的可控制备及其显著不同于棒状液晶聚合物体系的一些基本特征的阐明,为这类重要有机聚合物半导体材料的理性设计与可控合成提供理论指导,也为加速推进其光电器件化应用奠定基础.     

苯并䓛盘状液晶:合成、柱状相和光物理性质

盘状液晶分子由稠环芳核和围绕的多条柔性链构成, 具有独特的自组装有序超分子结构、半导体性质和光学性质. 其可通过溶液或喷墨打印技术加工成为光电子薄膜器件, 具有低成本优势. 通过Suzuki-Miyaura交叉偶联和Scholl氧化环化策略, 合成了一系列新的具有苯并䓛结构的非对称酸酐、羧酸酯、酰亚胺和苯并咪唑稠环衍生物, 并对其液晶性和光物理性质进行了详细研究. 通过偏振光学显微镜(POM), 差示扫描量热法(DSC)和小角度X射线散射(SAXS)测试表明, 这些极性盘状化合物自组装堆积呈六方柱状(Col_hex)液晶相, 其中, 最宽的液晶温度范围达206 ℃. 官能团和共轭体系大小决定了相变温度和液晶范围. 荧光测试结果表明, 化合物溶液中绝对量子产率高达34%, 根据官能团不同, 这些化合物发蓝、绿和红光. 借助密度泛函理论(DFT)计算, 解释了该系列极性盘状液晶分子发光性质的差异. 基于本工作的合成方法, 从萘酸酐原料出发为构建结构多变、性质丰富的π-共轭(杂环)芳烃盘状液晶化合物提供了新途径.     

钯催化偶联反应合成刚性桥连的苯并菲盘状液晶二聚体

盘状液晶是一类新型有机半导体材料, 盘状二聚体具有新颖的自组织特性. 合成了一系列官能化的盘状液晶单体, 再通过Pd催化端炔自身偶联反应合成了六个二苯基丁二炔桥连的苯并菲盘状液晶二聚体: (RO)₅C₁₈H₆(O₂CC₆H₄C≡C—C≡CC₆H₄CO₂)C₁₈H₆(OR)₅ (R＝C_nH_2n＋1, n＝4～9). 化合物的纯度和结构通过¹H NMR, IR和高分辨质谱表征. 二聚体的热失重分析(TGA)结果显示它们有良好的热稳定性, 在370 ℃才开始分解. 化合物的热致液晶性通过偏光显微镜和差视扫描热量法研究, 结果显示所有单体及二聚体化合物均为柱状相液晶, 在室温及以下仍处于液晶相. 单体清亮点随柔链增长呈下降趋势, 而二聚体呈相反趋势. 苯并菲柔链长度和连接基刚性对液晶性都有重要影响.     

刚棒中心含侧基的刚棒-线团分子的合成及聚集体结构分析

合成了一系列三嵌段刚棒-线团分子,这些分子由含有苯、联苯和具有侧基的苯单元与聚合度为7,12及17的不同长度烷氧基链组成.通过氢核磁共振仪(1H NMR)和质谱(MALDI-TOF MS)对其结构进行了表征,利用差示扫描量热法(DSC)、偏光显微镜(POM)和小角X射线散射实验(SAXS)对这些液晶化合物的自组装行为进行了研究.实验结果表明,侧基含酯基的分子1a~1c自组装成层状、倾斜柱状和六方穿孔层状结构;而侧基含羧基的分子2a~2c则自组装成倾斜柱状、体心四方聚集体.可见,随着烷氧基链长度的改变,刚棒中心的羧基和酯基能诱导分子的自组装行为发生变化.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col h ) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col_h) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Self-assembled discotic nematic liquid crystals formed by simple hydrogen bonding between phenol and pyridine moieties

New discotic nematic liquid crystals have been prepared through intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene (phloroglucinol, PG) or 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) and the peripheral molecules of stilbazole derivatives. The various nematic phases formed by new hydrogen bonding building blocks were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The first discotic complexes of PG and trans-4-alkoxy-4′-stilbazoles exhibited nematic columnar (N_C) and hexagonal columnar phases depending on the length of alkyl chains, which were considered as the basic discotic structure. Several structural variations on the building blocks were attempted to examine their effects on the liquid crystalline properties of discotic complexes. The nematic lateral phase (N_L) with enhanced intercolumnar order was observed for the complexes of PG and trans-4-cyanoalkoxy-4′ stilbazoles due probably to the strong dipole interactions between cyano groups at the end of alkoxy chains. By introducing the nonlinear structure in three arms of supramolecular discotic mesogen, a discotic nematic phase (N_D) was observed for the complex of THPB and trans-4-octyloxy-4 -stilbazole. The single hydrogen bonding between phenol and pyridine moieties in this study provides a simple and effective method for preparing the rarely found discotic nematic liquid crystals.     

A triphenylene-containing side chain liquid crystalline ladder-like polysiloxane and its highly ordered superstructure

A liquid crystalline discotic triphenylene-containing side chain ladder-like polysiloxane (LPS) derivative was prepared by hydrosilylation. The superstructure was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and isotherm surface pressure ( ∪)-area ( A ) diagrams based on LB-film experiments. The XRD results suggest that the discotic triphenylene units in the side chains stack to form a columnar structure and the columns further align with each other to form a board-like superstructure because of the semi-rigidity of the ladder-like backbone. This suggestion has been confirmed by parallel nanowire-like stripes observed in the AFM image. Mixing small amounts of the corresponding low molar mass molecules with the polymer leads to a more ordered and denser columnar stacking, as shown by sharpened XRD patterns and a ∪-A curve with a steeper slope, higher collapse pressure and lower collapse area than those obtained either for the low molar mass molecules or the polymer individually.     

Interplay between H‐Bonding and Alkyl‐Chain Ordering in Self‐Assembly of Monodendritic L‐Alanine Derivatives

This paper reports on the synthesis and self‐organizing properties of monodendrons consisting of L ‐alanine at the focal point and alkyl chains with different length at the periphery. The structures of thin films and monolayers are studied by temperature‐resolved grazing‐incidence X‐ray diffraction and scanning force microscopy. The interplay between H‐bonding and ordering of the alkyl chains results in a rich temperature‐dependent phase behavior. The monodendrons form H‐bonded stabilized clusters with the number of molecules depending on the length of the aliphatic chains and temperature. The clusters play the role of constitutive units in the subsequent self‐assembly. Short alkyl chains allow the material to form thermodynamically stable crystalline phases. The molecules with longer side groups exhibit additional transitions from the crystalline phase to thermotropic columnar hexagonal or columnar rectangular liquid‐crystalline phases. In monolayers deposited on highly ordered pyrolytic graphite, the materials show ordering similar to thin films. However, for the compound bearing hexadecyl chains the affinity of the alkyl groups to graphite dominates the self‐assembly and thereby allows epitaxial growth of a 2D lattice with flat‐on oriented molecules.     

Influence of peripheral alkyl chain length on the mesomorphic behaviours of hexasubstituted triphenylene 2,3-dicarboxylic esters

A comparative study of our established synthetic approaches to hexasubsituted triphenylenes 2,3-dicarboxylic esters containing four identical β-alkoxy and two adjacent β-alkoxycarbonyl side chains shows that the phase behaviours of small-sized discotic liquid crystals can be tailored over a wide range by simply varying the length of the peripheral alkyl chains. All the prepared esters in two series were observed to form a single hexagonal columnar phase, except for Tp4-1 having four β-butyloxy and two adjacent β-methoxycarbonyl chains which displays two columnar mesophase behaviours with a transition from the columnar plastic phase to hexagonal columnar phase. A significant difference between the two mesophase was observed in the variable temperature X-ray diffraction studies, and the mesophase assignment was also confirmed by polarising optical microscopy and differential scanning calorimetry. Moreover, the prepared esters in each series display the general trend of decreasing clearing temperature upon increasing alkoxy or alkoxycarbonyl chains length. The intermediate triphenylene 2,3-dicarboxylic acids were also found not only to exhibit columnar hexagonal mesophase over a narrower temperature range by maintaining high melting and clearing points but also to form organogel on mixing with toluene or dichloromethane with the assistance of hydrogen bonding.     

Self-assembly of discotic liquid crystalline molecule-modified gold nanoparticles: control of 1D and hexagonal ordering induced by solvent polarity

Gold nanoparticles fully coated with discotic liquid crystalline molecules of hexaalkoxy-substituted triphenylene (Au-TP) have been synthesised, the self-assembled structure of which could be controlled (hexagonal or 1D nanochain) just by altering the ratio of methanol to toluene in the solvent.     

Induction of a nematic columnar phase in a discotic hexagonal ordered phase forming system

The induction of a nematic columnar phase in a discotic hexagonal ordered phase forming system is achieved by mixing hexakispentyloxytriphenylene 1 with a long chain derivative of trinitrofluorenone 3. The difference in chain length has a strong influence on the packing behaviour due to steric effects. The long hydrocarbon chains of the acceptor introduce a strong asymmetry into the electron donor acceptor complex. It could be shown by differential scanning calorimetry, optical microscopy and X-ray measurements that a nematic columnar phase is formed. In this mesophase the triphenylenes form columns but no hexagonal or orthorhombic lattice is built up. Each column behaves like a rod-like nematic mesogen. To prove that the long hexadecane alkyl chains of the acceptor are responsible for this induction, the acceptor 3 was mixed with the non-liquid-crystalline triphenylene derivative 2 containing six hexadecyloxy side groups. The long alkyl chains of the acceptor dissolve perfectly in the side chain region of the discs. No asymmetry is induced and the columns formed can be arranged on a hexagonal lattice resulting in a D_ho phase.     

Discotic liquid crystalline materials for potential nonlinear optical applications: synthesis and liquid crystalline behavior of 1,3,5-triphenyl-2,4,6-triazine derivatives containing achiral and chiral alkyl chains at the periphery

As a novel approach to nonlinear optical materials, new octupolar discotic liquid crystalline materials 1,3,5-triphenyl-2,4,6-triazine derivatives containing achiral alkyl chains (5a) and chiral alkyl chains (5b) at the periphery were synthesized. The former exhibits an ordered hexagonal columnar mesophase, whereas the latter displays a rectangular columnar mesophase. The negative exciton splitting observed in the CD spectrum of a thin film of 5b suggests that it has a left-handed helical structure within the column.     

Self-assembly of liquid crystalline triphenylene-oligo(ethylene oxide)-triphenylene molecules and their complexes with lithium triflate

Mesomorphic dimeric molecules consisting of discotic triphenylene rigid units and flexible ethylene oxide spacers have been prepared. The liquid crystalline behaviour is greatly dependent on the length of the ethylene oxide chains. The miscibility and phase behaviour have been examined for mixtures of the materials with lithium triflate.