二芳基乙烯类光致变色材料的合成概述

由于具有多种潜在的应用价值, 光致变色化合物作为高级功能材料的研究在国内外广受关注. 在众多的有机光致变色化合物中, 二芳基乙烯特别是二噻吩乙烯, 由于其具有良好的热稳定性和优良的耐疲劳度而成为这类化合物的杰出代表. 近年来, 有关二芳基乙烯类光致变色化合物的各种合成及性能方面的报道已涉及到信息存储、分子开关、逻辑电路、液晶显示、磁性材料等众多领域. 主要是从有机合成的角度, 对这类材料的合成进行了较为全面的概括, 对各种合成方法分别加以介绍和分析, 对其发展趋势予以探索和展望.     

六芳基二咪唑类化合物的合成及光致变色性能

六芳基咪唑;六芳基二咪唑类化合物的合成及光致变色性能     

2,2-二芳基取代萘并吡喃类光致变色化合物的合成与性能研究

从光消色速度和最大吸收强度两个角度出发, 用Grignard试剂和萘并吡喃-2|酮合成了一系列2,2-二芳基取代萘并吡喃类光致变色化合物, 并用 1H NMR, IR, MS和元素分析确定其结构. 研究了其紫外-可见光谱, 并探讨了紫外-可见光谱和光致变色性能之间的关系, 分析了其结构和光消色速度之间的关系, 初步探索到光消色速度快慢和取代基位置之间的规律, 为实用化的有机光致变色化合物的合成提供了有价值的参考依据.     

萘并吡喃类固态光致变色化合物的合成及性能研究

合成了化合物 ２,２－二芳基萘并吡喃（２ａ－２ｐ）,产物结构和组成通过１Ｈ ＮＭＲ, ＭＳ和元素分析证实．测定了化合物光照前后的紫外可见吸收光谱．部分化合物表现出良好的固态光致变色性能,分析了它们的结构与光致变色性能间的关系．     

卟啉-二芳基乙烯分子及其金属配合物的合成与光致变色特性

以苯甲醛和吡咯为初始原料,经多步反应合成了5-[2,3-双(2,4,5-三甲基-3-噻吩基)马来酰亚胺-N-苯基]-10,15,20-三苯基卟啉(TPPMA)及其金属锌配合物(ZnTPPMA)与铜配合物(CuTPPMA),通过IR,MS,1H NMR和13C NMR确认了化合物的结构,并利用UV-Vis光谱探讨了化合物的光致变色性能.实验结果表明,无论在聚乙烯醇缩丁醛(PVB)膜还是在溶液中,TPPMA在254 nm紫外光照射下,没有光致变色现象,而在254和650 nm的光照下其金属配合物CuTPPMA和ZnTPPMA在溶液及PVB膜中皆可以发生可逆的光致变色反应.     

对称吡啶基二噻吩乙烯光致变色化合物的合成与性能

二噻吩乙烯光致变色化合物具有热稳定性高、抗疲劳性好等优点。 本文以2-甲基噻吩为原料,经过Suzuki偶联、傅克酰基化、McMurry环合3步反应制备1,2-二(5-吡啶基-2-甲基噻吩-3-基)环戊烯,总收率61%。 所有中间体及目标产物均已通过核磁共振、质谱、红外光谱等技术手段表征。 该合成方法具有合成步骤少、简便、总收率高、易于工业化生产等优点。 利用紫外-可见吸收光谱、荧光光谱对该化合物及其与镍离子、锡离子相互作用的光致变色性能以及应用进行了研究。 对称吡啶基二噻吩乙烯通过与金属配位在紫外光的照射前后显示出不同的颜色和光谱吸收,可以用作新型金属离子探针。     

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.     

含三苯胺基团的二噻吩乙烯光致变色化合物的合成及性能研究

以5-氯-2-甲基-3-乙酰基噻吩和二苯氨基苯甲醛为原料,经Aldol反应、Michael反应及McMurry反应,将光致变色单元和三苯胺基团结合起来,合成了三种二噻吩乙烯类光致变色化合物1a～1c,并通过MS,¹H NMR和¹³C NMR对其结构进行了表征.与以往主要从两侧噻吩环引入不同功能性基团的研究不同,本文将具有荧光性的三苯胺基团通过单键桥连至环戊烯β位上,在保持光致变色反应活性的同时,也避免其它功能性基团对二噻吩乙烯骨架的影响.通过紫外-可见吸收光谱和荧光光谱研究了其在溶液及聚甲基丙烯酸甲酯薄膜中的光致变色性能和荧光性能.在302 nm紫外光照射下,1a～1c的溶液和薄膜由无色变为黄色,并能快速达到光稳态;用450 nm蓝光照射时,能在较短时间内恢复至无色.在紫外光的激发下,1a～1c的最大荧光发射波长随着取代基R供电子效应的增强而增大;1a～1c在正己烷、甲苯和乙酸乙酯中具有较强的荧光,在乙腈中荧光较弱,而在氯仿中几乎没有荧光.在302 nm紫外光照射下,1a～1c的三苯胺基团和二噻吩环戊烯基团之间发生荧光共振能量转移,其荧光强度随着光照时间的延长逐渐降低,表明其具有作为荧光分子开关的潜力.     

光致变色全氟环戊烯类二芳烯化合物的合成及其性质研究

合成了两种新的二芳基乙烯类光致变色化合物1,2 双(2 甲基5 (4 乙氧基苯基)噻吩3 基)全氟环戊烯(1a)和1,2 双(2 甲基5 (对氟苯基)噻吩3 基)全氟环戊烯(2a),并且研究了其在不同溶剂和浓度中的UV Vis光谱、荧光性质和光致变色反应动力学特征.实验结果表明,化合物1a和2a具有良好的光致变色性质和较强的荧光;光致变色闭环反应为零级反应,开环反应为一级反应.     

2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

A High‐Content Diarylethene Photochromic Polymer for an Efficient Fluorescence Modulation

Summary: A highly fluorescent photochromic polymer, poly‐BTFO4, was prepared. The fluorescence quantum yield of the poly‐BTFO4 was six times higher than that of BTFO4. Fatigue resistance of the polymer at its photostationary state was significantly enhanced compared with that of BTFO4. Importantly, the poly‐BTFO4 film also showed an efficient photochromism as well as strong fluorescence similar to the results in solution, which allow photoinduced fluorescence switching applicable to optical switches.

Improvement of fluorescence quantum yield and fatigue resistance.     

萘并吡喃光致变色荧光开关研究进展

萘并吡喃及其衍生物是经典的光致变色材料,具有很低的背景颜色、优良的光致变色抗疲劳性、易于调控的变色动力学、开环体具有宽的吸收等优点,受到了研究者的重视。本文综述了近几年来作者课题组利用萘并吡喃构建光致变色荧光开关的研究进展,通过将荧光基团和萘并吡喃以掺杂模式、共聚物和有机小分子等形式构建光致变色荧光开关,研究了它们在溶液和薄膜中的荧光开关性能,初步探讨了萘并吡喃荧光开关在非破坏性读出和荧光成像等方面的应用潜能。     

Photochromic 1,2-dihetarylethenes with perfluorocyclopentene bridge: Synthesis and spectral and kinetic study

A spectral and kinetic study was carried out of some substituted 1,2-dithienylperfluorocyclopentenes and 1,2-bis(benzo[b]thienyl)perfluorocyclopentenes suitable for use as photosensitive components of photochromic recording media for optical memory. The introduction of nitro groups into the benzothienyl moieties dramatically decreases photodegradation and increases the fatigue resistance of these photochromes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2697–2700, December, 2005.     

Solid‐State Photochromic Behavior and Thermal Bleaching Kinetics of Two Novel Pyrazolone Phenylsemicarbazones

Two novel photochromic compounds, 1,3‐diphenyl‐4‐benzal‐5‐hydroxypyrazole 4‐phenylsemicarbazone ( 1 a ) and 1,3‐diphenyl‐4‐(4‐nitrobenzal)‐5‐hydroxypyrazole 4‐phenylsemicarbazone ( 2 a ), are synthesized and characterized by elemental analysis, mass spectrometry, FTIR spectroscopy, and ¹H NMR spectroscopy. Their properties, including photochromic behavior, fluorescence properties, and thermal bleaching kinetics, are investigated. The results show that the two compounds exhibit improved photochromic performance in coloration and thermal bleaching rates, excellent photostability, high fatigue resistance, and reversible fluorescence switching properties in the solid state in comparison to reported pyrazolone thiosemicarbazones. The thermal bleaching process obeys first‐order kinetics. Bleaching of powders at 130 °C is completed within 90 s for 1 b (the colored isomer of 1 a ) and 150 s for 2 b (the colored isomer of 2 a ). The activation energy for the thermal bleaching process is determined to be 69 and 95 kJ mol^?1, with frequency factors of 9.5×10⁷ and 9.4×10¹⁰ s^?1 for 1 b and 2 b , respectively.     

1-(2-螺二芴)-3,4-二[3-(2,5-二甲基呋喃)-2,5-二氢吡咯的合成及光致变色性质的研究

将螺二芴引入二芳基乙烯分子中,设计合成了一种新型的含螺二芴呋喃芳香杂环的二芳基乙烯光致变色分子7a.用FT-IR,NMR,MS和元素分析进行结构表征;研究了7a在正己烷溶液和乙腈溶液中的光致变色反应,结果表明7a在两种溶剂中均具有良好的光致变色性能.并且7a在正己烷溶液中变色速率和转化率比在乙腈溶液中大.还研究了7a光致变色过程中荧光光谱的变化,发现关环反应后荧光被淬灭,并且7a的荧光发射峰在极性溶剂中有很大的蓝移.研究了开环态7a,关环态7b的热稳定性,发现7a的热失重温度比未用螺二芴修饰的8a提高了100℃.7b的热稳定性也比8b高.     

Synthesis and Crystal Structure of 1-(2-Methyl-5-formyl-3-thienyl)-2-(2-methoxylphenyl)perfluorocyclopentene

A new family of photochromic diarylethene compounds, 1-(2-methyl-5-formyl-3- thienyl)-2-(2-methoxylphenyl)perfluorocyclopentene (1o) having an unsymmetrically substituted hexafluorocyclopentene unit, was synthesized and its structure was determined. The crystal belongs to the monoclinic system, space group P21/c with a = 15.4866(5), b = 9.0744(9), c = 12.6906(3), β = 90.1480(10)°, Z = 4, V = 1783.4(3)3, Dc = 1.513 mg/m3, μ = 0.25, F(000) = 824, the final R = 0.0579 and wR = 0.1566 for 2584 observed reflections (I > 2σ(I)). Interestingly, a colorless compound 1o undergoes photocyclization upon irradiation of UV light to give the blue isomer diarylethene. Upon irradiation with visible light with wavelength greater than 510 nm, the blue compound can return to its initial colorless state.     

A Combination of Selective Light Reflection and Fluorescence Modulation in a Cholesteric Polymer Matrix

Summary: The phase behavior and optical properties of a cholesteric ternary copolymer, containing nematogenic phenylbenzoate, cholesteric, and photochromic diarylethene side groups, and its mixture with 2 wt.‐% fluorescent dopant were studied. The investigation of the kinetics of a photochemical opening‐cycle process of the photochromic groups in the cholesteric mixture proved the energy transfer from the fluorescent dopant to the photochromic diarylethene groups. It was shown that the fluorescence intensity of the fluorescent dopant could be controlled by the portion of the “closed” form of the diarylethene groups. During the photocyclization of the photochromic groups a “degeneration” of the selective light reflection of the cholesteric matrix is observed.

Fluorescence‐resonance energy transfer makes possible the process of photosensitization of the back ring‐opening photoreaction of the photochromic diarylethene groups in the cholesteric polymer matrix.     

Synthesis and Properties of a Novel Photochromic Compound

A new photochromic compound containing pyrazolone-ring was synthesized, and its crystal structure was determined on X-ray singlecrystal diffraction, which belongs to monoclinic crystal system, space group P21/c. The UV spectrum of the compound is studied.