低相变温度锌卟啉液晶的合成与表征

卟啉液晶作为一种功能型盘状液晶,已经受到了科学家们的高度重视^[1]。自1980年Goodby^[2]首次合成出简单的卟啉液晶以来;各国学者对卟啉液晶的合成做了相应的研究工作,但其液晶相变温度偏高^[3,4],相区宽度偏窄^[3]。本文首次合成出相变温度较低,相区宽,含有8,10,12和14碳的酰氧基的四种卟啉液晶5、10、15、20－四（对－酰氧基）苯基卟啉液晶5、10、15、20－四（对－酰氧基）苯基卟啉锌（Ⅱ）配合物[分别简称为TOPPZn,TDPPZn,TLPPZn,TMPPZn]。研究4种配合物的液晶行为,其液晶相相变温度最低始于－36．4℃,相区宽达175℃,是一种具有应用前景的卟啉液晶。     

4-(2-甲基-丁氧基)苯甲酰氧基-4′-苯甲酰氧基苯基卟啉的合成

四 (对羟基苯基 )卟啉 [Ｔ( 4 ＨＰ)Ｐ]具有共扼大π键及刚性平面 ,在 65 0ｎｍ左右产生纯的红色荧光 ,是一种较好的发光材料。依据 4 ( 2 甲基 丁氧基 )苯甲酚氧基 4′ 苯甲酰氧基苯基穴醚 [2 .2 ]具有液晶性[1 ] ,本文设计使Ｔ( 4 -ＨＰ)Ｐ的羟基进行酯化反应后生成的卟啉衍生物同时具有荧光和液晶性质 ,估计在发光材料特别是新近出现的圆偏光电致发光材料中具有潜在的应用[2 ] 。反应混合物通过柱色谱分离得到了酯化程度不同的几种卟啉衍生物。合成路线如下1　实验1 1　仪器及试剂Ｐｅｒｋｉｎ Ｅｌｍｅｒ1 70 0红外光谱仪 ,ＫＢｒ压…     

新型meso-四(4-N-n-十二胺基磺酰苯基)四苯并卟啉的合成及其液晶性能

苯乙酸锌和邻苯二甲酰亚胺反应制得meso-四苯基四苯并卟啉锌(1);1酸化得meso-四苯基四苯并卟啉(2);2经氯磺化生成meso-四(4-氯磺基苯基)四苯并卟啉(3);3与n-十二胺反应合成了一种新型的苯并卟啉类化合物--meso-四(4-N-n-十二胺基磺酰苯基)四苯并卟啉(4),其结构经UV-Vis,<'1>H...     

中位-四-(对十六酰氧基苯基)卟啉及其锌配合物的合成、 表征与液晶性

首次合成出中位-四-(对十六酰氧基苯基)卟啉(TPPPH2)及其锌配合物(简称TPPPZn),研究了其液晶性质,结果表明这种卟啉及其锌配合物具有液晶性质。     

meso-四(邻烷氧基苯基)卟啉合钴的合成、表征和性能研究

合成了meso-四(邻烷氧基苯基)卟啉合钴配合物10个,其中未见文献报道的新化合物8个，研究了其合成、分离、纯化方法,首次得到了该系列化合物的晶体或固体。用¹H NMR、MS、IR、UV、元素分析等表征确证了其结构,报道和解析了该类卟啉钴配合物的¹H NMR特殊波谱现象。用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性。研究了烷氧基链长、金属离子和分子空间结构对卟啉液晶性能的影响,烷氧基链长的增加、金属配合物的形成有利于液晶性能的改善。     

meso-四(对烷氧苯基)卟啉金属配合物的合成和性能研究(Ⅲ)

合成了Ni系列卟啉金属配合物10个,其中6个为未见文献报道的新化合物,用元素分析、IR、UV、1H NMR、MS确证了其结构.总结了Ni与卟啉类配体配合的IR、UV、1H NMR判据.研究了该系列化合物的液晶性能,发现5个化合物具有液晶性.考察了烷氧基链长及配位金属离子对液晶性能的影响.发现带有10个碳原子以上的烷氧基链的配合物具有液晶性.     

meso-四(间烷氧基苯基)卟啉及其铜配合物的合成、 表征和性能研究

设计合成了meso-四(间烷氧基苯基)卟啉及其19个铜配合物, 其中16个为未见报道的化合物. 研究了其合成、分离、纯化方法, 得到了这两个系列化合物的晶体或固体, 其结构经 1H NMR, MS, IR, UV和元素分析确证. 研究了这两个系列化合物的液晶性能, 发现13个化合物具有液晶性, 其液晶行为表现为升温单变液晶. 还研究了烷氧基链长、金属离子和分子空间结构对卟啉化合物液晶性能的影响.     

meso-四(对烷氧基苯基)卟啉镁配合物的合成、表征和性能研究

合成了一系列meso-四(对烷氧基苯基)卟啉镁配合物,用UV-Vis,1H NMR,IR,MS,元素分析等确证了配合物的结构,总结了镁与卟啉类配体配合的UV-Vis,1H NMR,IR数据.采用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性;考察了烷氧基链长、配位金属离子和分子空间结构对液晶性能的影响.     

丝状液晶5CB与铁(Ⅲ)卟啉之间的轴向配位作用

通过考察掺杂配位性质不同的两种铁(Ⅲ)卟啉的丝状液晶5CB在磁场下的行为以及UV-Vis光谱,研究了液晶5CB与铁(Ⅲ)卟啉的轴向配位作用.结果表明,弗雷德里克兹转变阈值的降低和Soret带随着液晶5CB含量增大而红移是液晶5CB与五配位Fe(TPCl发生轴向配位的结果.     

对烷氧基苯基苯并卟啉的新法合成及性能研究

采用先接链后合环密闭熔融新方法，合成了５个系列２５种对烷氧基苯基苯并卟啉，通过紫外，红外，质谱和元素分析等手段进行了表征，初步研究了１０种新型卟啉的性能。     

液晶离聚物的合成

由于液晶离聚物需要在液晶聚合物中引入离子基团，因此造成了合成上的困难，有关液晶离聚物的合成还处于探索阶段。本文综述了液晶离聚物的合成方法，并描述了这些方法所获得的液晶离聚物的规律性的液晶行为。     

Synthesis and Mesogenic Properties of Novel Terthiophene Derivatives

To develop novel oligothiophene‐based liquid crystals involving hydrogen bonding, new terthiophene derivatives containing a stearylamide group, N,N′‐distearyl‐5,5″‐dicyano‐2,2′∶5′,2″‐terthiophene‐4,4″‐dicarboxamide (DNC₁₈DCN 3T) and N,N′‐distearyl‐5,5′‐dipropyl‐2,2′∶5′,2′‐terthiophene‐4,4″‐dicarboxamide (DNC₁₈ DP3T), were designed and synthesized, and their thermal behavior examined. Although DNC₁₈DP3T did not exhibit liquid crystallinity, DNC₁₈DCN3T was found to form smectic A phase.     

SYNTHESIS AND PROPERTIES OF LIQUID CRYSTAL POLYSILOXANES WITH MESOGENIC STILBENE SIDE GROUPS*

A variety of mesomorphic side-chain polysiloxanes were synthesized by using hydrosilylation reaction withdicyclopentadienylplatinum (Ⅱ) (DPPC) as the catalyst. The mesogenic groups are derivatives of stilbene with cyano or nitrotail groups. The products were characterized by DSC, X-ray deffraction and polarizing optical microscopy (POM). All thepolymers were found to have relatively low T_g and can form a smectic liquid crystal phase.     

Synthesis and characterization of cross-conjugated cruciforms with varied functional groups

A series of novel oligo(p-phenylenes) (OPPs) derivatives with bisdiene side-chains are synthesized and fully characterized. These cruciforms are soluble in common organic solvents and show good thermal stability. Absorption and emission spectra are recorded to study the effect of different electron-withdrawing and electron-donating groups on photophysical properties. Powder XRD shows crystalline structures for all the cruciforms. Single crystal XRD studies show tight-packing along the planar bisdiene axis but significant twisting along phenylene units, which correlate the role of functionalization along the bisdiene axis in tuning the band gaps of the cruciforms.     

两个新的氢键诱导液晶化合物的合成

通过４－丁氧基苯甲酸（４ＢＡ０与两个手性取代的苯乙烯基吡啶（ＶＳＺ及ＬＳＺ）间的氢键作用合成了２个新的液晶化合物，用ＤＳＣ、偏光显微镜研究了其液晶行为，并由红外光谱证实了分子间氢键的存在，形成的复合物４ＢＡ－ＶＳＺ具有手性近晶Ｃ相。     

Synthesis and mesomorphic properities of some ferroelectric liquid crystals of lactate

A semiperfluorinated chain has been introduced into three series of lactate-based molecules,and their mesomorphic properities have been studied by DSC and optical polarized microscope.An abnormal phenomenon has been found that the introduction of a triple bond in the core of the molecule,which lengthened the molecule,gave rise to a decrease in the thermal stability of chiral smectic C phase and smectic A phase.2,3-Difluoro substituents of the phenylenic structure hinder the formation of the chiral smectic C phase because of the steric effect.     

Synthesis and mesomorphic properties of some ferroelectric liquid crystals of lactate

A semiperfluorinated chain has been introduced into three series of lactate‐based molecules, and their mesomorphic properties have been studied by DSC and optical polarized microscope. An abnormal phenomenon has been found that the introduction of a triple bond in the core of the molecule, which lengthened the molecule, gave rise to a decrease in the thermal stability of chiral smectic C phase and smectic A phase. 2, 3‐Difluoro substituents of the phenylenic structure hinder the formation of the chiral smectic C phase because of the steric effect.     

Synthesis and thermal behaviour of new poly(azomethine-ether)

A new poly(azomethine-ether) was synthesized by the reaction of bisphenol A with a thermotropic azomethine monomer, namely 4,4′-oxy-bis(4-chlorobenzylideneimino phenylene). In order to understand the influence of the molecular weight on the thermal properties, four fractions were isolated from the initial polymer. They were investigated by elemental analysis and spectroscopic methods (IR, UV, ¹H NMR) and their thermal behaviour was studied by differential scanning calorimetry, optical microscopy, thermogravimetrical analysis. An increase of the thermal transition temperatures and mesophase order with increasing molecular weight was noticed.     

Stability of liquid crystal micro-droplets based optical microresonators

Liquid crystal (LC) based tuneable optical microresonators are potential for being used as crucial components in photonic devices. In this article, we report experimental studies on LC micro-droplets dispersed in several dispersing media. We find that the size of the micro-droplets formed in a low refractive index and optically transparent perfluoropolymer are most stable with time than commonly used dispersing media. Using a negative dielectric anisotropy nematic liquid crystal, we show that the whispering gallery mode optical resonance properties such as the quality factor and the free spectral range of stable micro-droplets are independent of the strength of the applied electric field. The optical resonance properties under applied field are significantly different than that of the liquid crystals with positive dielectric anisotropy and are explained based on the elastic deformation of the micro-droplets.     

聚合物分散液晶(PDLC)材料的光聚合反应

以Ar+激光器为光源, 采用虎红、 N-苯基甘氨酸、二季戊四醇羟基五丙烯酸酯和乙烯基吡咯烷酮分别作为光引发剂、共引发剂、预聚物和稀释剂, 与液晶材料TEB30A结合, 通过光聚合反应, 制备了聚合物分散液晶(PDLC), 用紫外光谱和荧光光谱对其反应机理进行了分析. 实验结果表明, PDLC是通过光引发剂吸收光子能量后与共引发剂相互作用, 形成自由基中间体并引发聚合反应, 使预聚物与液晶产生相分离形成的.