3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮衍生物的合成，晶体结构与固态光致变色及光致自由基性质研究

本文合成了一系列3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮新化合物,并通过¹H NMR, IR, MS 和元素分析数据进行了结构表征,其中化合物1,5,6的结构通过单晶X-Ray衍射进行了确证。分别用固体紫外光谱和电子自旋共振光谱研究了化合物的光致变色性能和光致自由基性质,结果表明：该类化合物在200W高压水银灯光源照射下产生光致变色现象,同时具有光致自由基性质。本文还根据分子结构和及分子内的作用力讨论了性质与结构之间的关系。     

基于光致变色的联茚满烯二酮衍生物的新型光调控磁性的分子基磁体的合成及性能

分子基磁性材料,可用于信息存储、磁成像、光磁开关等.因此,分子基磁体设计与合成一直是当今科学研究的热门课题.受分子基磁体的启发,本研究合成了新型光调控磁性的分子基磁体含有2-硝基丙烷自由基和2,2,6,6-四甲基-1-氧基哌啶(TEMPO)自由基的联茚满烯二酮衍生物4.化合物4的合成方法为,以光致变色的7,7'-二甲基-3,3'-二乙基-3,3'-二羟基-2,2'-二茚叉基-1,1'-二酮(1)为起始原料,经过溴代反应,得到7,7'-二(溴代甲基)-3,3'-二乙基-3,3'-二羟基-2,2'-二茚叉基-1,1'-二酮(2).化合物2和2-硝基丙烷在乙醇钠的乙醇溶液中反应得到含有2-硝基丙烷自由基和醛基的联茚满烯二酮衍生物3.根据1H NMR,MS和元素分析对化合物3的结构分析表明,2-硝基丙烷基团和化合物3苯环上的亚甲基相连.对化合物3的1H NMR和ESR波谱进一步的分析表明2-硝基丙烷基团上存在单电子自旋.在化合物3的基础上,稳定的氮氧自由基TEMPO被成功地引入光致变色的联茚满烯二酮衍生物的苯环上得化合物4.对化合物2,3和4光照前后的性质变化进行了研究.固态化合物2,3和4光照下皆可发生光致变色;固态化合物2光照后可测得ESR波谱;固态化合物3和4光照前后皆可测得ESR波谱,且光照前后ESR波谱发生变化.磁化率测试表明,固态化合物4光照前后皆具有反铁磁性,且光照后反铁磁相互作用增强.测试结果表明固态化合物3和4光照后有两个或三个自旋中心,分别是2-硝基丙烷或TEMPO自由基以及光照产生的来自于联茚满烯二酮的羰基上的自由基.固态化合物4的颜色和磁性可用光调控.     

有机光致变色自由基化合物研究进展

综述了近年来有机光致变色自由基化合物的研究进展, 着重介绍了联茚满烯二酮类自由基衍生物的发展. 对自由基的生成和变色机理做了较为细致的介绍.     

5,5′-二甲基-2,2′-二茚满-1,1′,3,3′-四酮的合成及结构表征

2,2′-二茚满-1,1′,3,3′-四酮(1)是合成茚满类光致磁性材料[1]的重要中间体, 在军事目标识别、特殊防伪以及光信息存储等领域具有潜在的应用价值, 因此取代的2,2′-二茚满-1,1′,3,3′-四酮的合成已成为人们研究的焦点.     

联烯的自由基反应

联烯是含有1,2-丙二烯官能团的重要化合物,具有很高的反应活性.概述了联烯及其衍生物的自由基反应,包括分子间自由基链加成和分子间-分子内自由基串联加成反应,及其在天然产物中的应用.联烯进行分子间自由基链加成反应时,自由基对联烯的加成既可发生在中间碳原子上,也可发生在末端碳原子上,主要取于所形成中间体的稳定性,空间效应、电负性和溶剂等因素也有影响.一般以碳为中心的自由基(如CH3·,CCl3·等)易进攻末端碳原子,而以杂原子为中心的自由基(如Br·,RS·,ArSO2·等)易进攻联烯的中心碳原子.联烯及其衍生物也易与烯烃、联烯、烯炔和乙烯酮进行[2 2]环加成反应,还可以与卡宾环丙烷化,这些反应都是通过自由基机理进行的.     

以β-二酮连接的含生色团丙烯酰类单体及其饱和模型化合物的荧光行为

通过合成一系列同一分子中既含有给电子性荧光生色团又含缺电子性碳碳双键的烯类单体, 发现这类单体在相同生色团浓度下的荧光强度均明显低于相应的饱和模型化合物或聚合物[1～3]. 这种现象称为荧光结构自猝灭效应(SSQE), 以区别于浓度自猝灭现象. 对于电子状态与之相反的单体, 即含受电子性荧光生色团的乙烯基醚类单体, 也观察到了SSQE[4,5]. 进一步的研究结果表明, SSQE是光照条件下分子内电子给受体之间电荷转移作用的结果, 分子中电子给受体间的间隔基长度和溶剂的性质等都对SSQE有显著的影响[6]. 以往合成的含给生色团的丙烯酰类单体, 其电子给受体间是通过饱和脂肪链相连, 当生色团和受电子性碳碳双键之间以β-二酮结构相连时, 这类单体的荧光性质如何, 是否发生SSQE是我们的关注所在. 另一方面, β-二酮类化合物在一定波长光照射条件下, 常发生烯醇式与酮式的互变异构化. 虽然已有许多文献报道有关烯醇式-酮式互变异构过程中各种光谱的变化以及用核磁、红外、紫外等光谱手段研究烯醇式-酮式互变异构动力学, 但有关β-二酮类化合物互变异构过程中荧光光谱的变化的报道却很少[7～11]. 本文合成了以β-二酮连接的含二甲氨基苯基生色团的烯类单体, 1-(4-二甲氨基苯基)-4-甲基-4-戊烯-1,3-二酮(DMPDK)及其饱和模型化合物1-(4-二甲氨基苯基)-1,3-丁二酮(DMBDK), 研究了其光谱性质及光致互变异构行为.     

喹啉季铵盐和1,3-茚满二酮及2-芳亚甲基1,3-茚满二酮的环加成反应合成茚满酮类含氮杂环化合物（英文）

在三乙胺存在下, N-苯甲酰基甲基喹啉溴化物和1,3-茚满二酮在乙醇中于室温反应,主要产物为多取代二氢吡咯[1,2-a]喹啉,次要产物为2-(1-苯甲酰基甲基)喹啉-4-亚基)-1,3-茚满二酮.在相同条件下,N-苄基喹啉溴化物和1,3-茚满二酮在乙醇中于室温反应,主要产物则为2-(1-苯甲酰基甲基)喹啉-4-亚基)-1,3-茚满二酮.另一方面, N-苯甲酰基甲基和N-乙氧羰基甲基以及N-(对硝基苄基)喹啉溴化物和芳香醛,1,3-茚满二酮的三组分反应,在三乙胺存在下在乙醇中高效地生成螺[茚满-2,3'-吡咯[1,2-a]喹啉]衍生物,反应具有很好的非对映选择性.     

光致变色液晶聚合物的光致再取向性能研究进展

光致变色分子经掺杂或键合作用嵌在液晶聚合物中可形成光致变色液晶聚合物,在线性偏振光或非偏振光的照射下,此物质中光致变色分子的构型变化会引起整个液晶分子的二维或三维光致再取向的形成,本文综述了光致变色液晶聚合物的光致再取向的近期研究进展.     

1,3,4-噁二唑键联二芳基乙烯化合物的合成及性质

将1,3,4-噁二唑基团引入二芳基乙烯分子中, 合成了2种新的二芳基乙烯类光致变色化合物1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯(3)和1,4-二{[1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯]-1,3,4-噁二唑}苯(4). 通过IR, NMR, MS和元素分析对化合物进行了结构表征, 并研究了其UV-Vis吸收、荧光发射、动力学特性和抗疲劳性质. 实验结果表明, 化合物[STHZ]3[STBZ]和[STHZ]4[STBZ]具有良好的光致变色性质, 光致变色闭环反应为零级反应, 开环反应为一级反应.     

串联合成新型色烯-茚二酮类化合物

报道了一种合成新型色烯-茚二酮类化合物3的方法.该反应以简单易得的2-羟基查尔酮(1)和1,3-茚二酮(2)为原料,以甲苯为溶剂在无催化剂条件下进行反应.所有化合物的结构都通过了1H NMR,13C NMR,IR和HRMS的表征.该反应的可能机理为分子间迈克尔加成/分子内环化/氧化的串联过程.目标产物3a~3h的紫外最大吸收波长在464~482 nm之间.     

A New Biindenylidenedione Compound with Two Azobenzene Units:Synthesis and Photochromic Behavior Both in Solution and in the Solid State

A new photochromic biindenylidenedione compound bearing two azobenzene units was synthesized and characterized by means of ¹H NMR, ¹³C NMR, ESI‐MS and elemental analysis. The photochromic and photo‐induced radical properties were investigated by means of UV‐Vis and electron spin resonance spectroscopy, respectively. The results showed that the title compound exhibited photochromic behavior with good fatigue resistances both in solution and in the solid state.     

Synthesis,photochromic mechanism and properties of a novel biindenylidenedione compound containing ferrocene units

A novel biindenylidenedione compound, [2,2′‐bi‐1H‐indene]‐3,3′‐bis [(4‐oxo‐4‐ferrocenylbutanoyloxy)propyl]‐3,3′‐ dihydroxy‐1,1′‐dione was synthesized and characterized fully by ¹H NMR, IR, MS and elemental analysis. The photochromic and photo‐induced radical properties were investigated by means of UV–vis and electron spin resonance spectroscopy, respectively. The results show that the title compound simultaneously exhibits photochromism in the solid state as well as generating stable free radicals under irradiation with 330 nm light. This fact provides evidence for the photochromic mechanism of this kind of compounds. Copyright © 2008 John Wiley & Sons, Ltd.     

Thermal and Emission Properties of a Series of Lanthanides Complexes with N-Biphenyl-Alkylated-4-Pyridone Ligands: Crystal Structure of a Terbium Complex with N-Benzyl-4-Pyridone

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, ¹H, ¹³C NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 °C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).     

Synthesis and crystalline state photochromism of 3,3′-diaryl biindenylidenedione derivatives

A new series of 3,3′-diaryl biindenylidenedione derivatives were synthesized through Grignard reaction. Some of their stereoisomers were obtained by photochemical transformation upon heating and a plausible reaction mechanism was proposed. Most of these compounds exhibited photochromism in crystalline states as well as generation of stable organic radicals. The absolute configurations of the stereoisomers were determined by single crystal X-ray crystallography. The results showed that the position of substituent could dramatically affect molecular structure and photochemical properties of the biindenylidenedione derivatives.     

Properties of meso-tetrakis (4-n-alkanoyloxyphenyl) porphyrin liquid crystal Co and Ni complexes

Six series of meso-tetrakis (4-n-alkanoyloxyphenyl) porphyrin Co and Ni complexes (12 kinds) were reported. Nine of the compounds were found to exhibit liquid crystal properties and display a hexago-nal columnar discotic columnar (Colh) phase. Molecular structure of all synthesized compounds was confirmed by IR, UV, MS, 1H NMR, and elemental analysis. These liquid crystalline compounds have been studied by cyclic voltammetry, luminescence, and surface photovoltage spectroscopy.     

侧链型Schiff碱液晶研究——单体的合成与聚合

对具有Ｎ－（对甲基丙烯酰氧基苄叉基）取代苯胺骨架的一系列侧链型Ｓｃｈｉｆｆ碱液晶单体合成进行了研究，苯胺环上的取代基为卤素、强吸电子基及大体积基团，考察了取代基对液晶性质的影响。当取代基为４－氯，４－溴时，单体呈狭窄之液晶区间，而２，４－二氯取代物则无液晶性。当苯胺环上带有４－苯基的单体时，都呈宽的液晶区间。同时还对相应单体的自由基聚合及聚合物的相行为进行了研究。     

Design,synthesis, and characterization of a combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymer via atom transfer radical polymerization

A novel combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymers (MJLCPs) containing two biphenyls per mesogenic core of MJLCPs main chain, poly(2,5‐bis{[6‐(4‐butoxy‐4′‐oxy‐biphenyl)hexyl]oxycarbonyl}styrene) (P1–P8) was successfully synthesized via atom transfer radical polymerization (ATRP). The chemical structure of the monomer was confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymer with different molecular weights (P1–P8) were performed with ¹H NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase transitions and liquid‐crystalline behaviors of the polymers were investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM). We found that the polymers P1–P8 exhibited similar behavior with three different liquid crystalline phases upon heating to or cooling in addition to isotropic state, which should be related to the complex liquid crystal property of the side‐chain and the main‐chain. Moreover, the transition temperatures of liquid crystalline phases of P1–P8 are found to be dependent on the molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7310–7320, 2008     

Synthesis and characterization of a novel liquid‐crystalline epoxy resin combining biphenyl and aromatic ester‐type mesogenic units

A novel liquid‐crystalline epoxy resin combining biphenyl and aromatic ester‐type mesogenic units, diglycidyl ether of 4,4′‐bis(4‐hydroxybenzoyloxy)‐3,3′,5,5′‐tetramethyl biphenyl, was synthesized. Its spectroscopic structure, thermal properties, and phase structures were investigated with NMR, differential scanning calorimetry (DSC), and polarized light microscopy (PLM), respectively. The curing agent, diaminodiphenylsulfone, was chosen to investigate the curing behavior by means of DSC and PLM during isothermal and nonisothermal processes. Only one exothermal peak appeared in the isothermal DSC curves. Birefringence was also observed during the curing processes and preserved after postcuring. Compared with short rigid‐rod and flexible epoxies, the cured liquid‐crystalline epoxy resin that was obtained displayed special thermal stability according to thermogravimetric analysis because of its long rigid‐rod mesogenic unit and bulky methyl groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 727–735, 2007     

2,3-二氟代联苯类液晶化合物的合成与性能

以4-烷基环己基甲酸和4-溴-2,3-二氟苯酚为原料,经格氏、黄鸣龙还原、碘代、芳基硼酸化、Suzuki偶联、威廉姆逊和酯化等反应,合成24种侧向二氟取代联苯类液晶化合物,总收率4.2%～8.7%,产物的分子结构经核磁（1H NMR,13C NMR）、红外和质谱确认。 利用差示扫描量热仪（DSC）和偏光显微镜（POM）对目标化合物进行了液晶性能测试。 结果表明,烷基链的长度不仅影响化合物的熔点和清亮点,还影响液晶相态变化;端烯可以降低化合物的熔点（降低了3.7 ℃）,提高清亮点（提高了24.8 ℃）,拓宽向列相区间（由54.1 ℃拓宽到82.6 ℃）;酯基的引入可以提高清亮点,有助于消除近晶相。 该系列化合物在垂直取向(VA)和平面转换(IPS)显示模式中具有潜在的应用前景。     

Novel antiferroelectric liquid crystals with a phenylpiperazine moiety in the mesogenic core structure

A novel series of antiferroelectric liquid crystalline compounds having a phenylpiperazine unit and a biphenyl or a phenyl moiety in the core structure was synthesized using the optically active alcohols 2-methyl octanol and 1,1,1-trifluoromethyl octanol. Most of the compounds exhibited enantiotropic SmC*A, SmC* and SmA mesophases. The phase transition temperatures, response times, sponta A neous polarizations and the field-transmittance hysteresis loops were monitored. These data were compared with those of the MHPOBC compounds, which represent the most conventional core structure of the biphenyl/phenyl combination. The replacement of the biphenyl moiety, with the phenylpiperazine unit, reduced the isotropization temperature as well as the SmC*A-SmC transition point. It was found that some of the new compounds, which consisted ofAan octyl or a nonyl terminal chain with a 2-methyloctyl 2-fluorophenylcaboxylate group in the core structure, could have a potential application in display devices. Some work on blends of these compounds is also described.