含席夫碱基的螺噁嗪类光致变色化合物的合成及性质

设计合成了一系列含席夫碱基的螺噁嗪双功能光致变色材料4a~4d. 通过¹H NMR, ¹³C NMR, IR和HRMS对其结构进行了表征. 新化合物在几种有机溶剂中均表现出了良好的光致变色性. 研究了化合物在几种高分子膜中的光致变色性. 比较了化合物4b的开环体在两种不同溶剂, 即甲醇和二甲亚砜, 以及3种高分子介质, 即聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇缩丁醛(PVB)和聚乙烯醇(PVA)中的消色速率. 研究了化合物在甲醇、二甲亚砜、PMMA及PVB中的消色过程动力学, 根据化合物在溶液中和高分子介质中开环体消色过程的差别, 推测了存在两种动力学解释的原因. 研究结果显示, 化合物4d在PMMA膜中的耐疲劳度良好.     

含席夫碱基的螺吡喃双功能光致变色材料的合成及性质

设计合成了一系列含席夫碱基的螺吡喃双功能光致变色材料4a~4n. 通过1H NMR, IR和HRMS对其结构进行了表征. 研究了化合物在几种溶剂和PMMA膜中的光致变色性质, 研究了化合物4a在甲醇中, 以及化合物4a和4f在高分子介质聚甲基丙烯酸甲酯(PMMA)中的消色过程. 结果表明, 化合物4e在PMMA膜中光照后呈现出与其它化合物不同的颜色, 为罕见的绿色. 化合物4a在二氯甲烷溶液中有良好的荧光性能. 所合成的新型含席夫碱基的螺吡喃双功能光致变色材料在甲醇、二氯甲烷和环己烷溶液中及在PMMA膜中均表现出良好的光致变色性质.     

新型含氮杂环螺吡喃化合物的合成及性能研究

为了改善螺吡喃的光致变色性能,提高这一系列化合物的耐疲劳度,在螺吡喃吲哚啉环的氮原子上通过短碳链引入含氮杂环基团,成功合成了1'-(3-N-杂环基丙基)-3',3'-二甲基-6-硝基螺[吲哚啉-2,2'(2H)苯并吡喃](4a～4f).这一系列新的化合物.用核磁共振氢谱、碳谱、红外光谱和元素分析对这些化合物进行结构表征.通过紫外吸收光谱研究化合物在不同溶液(乙醇、二氯甲烷和环己烷)中和不同高分子膜(PMMA和PVB)中的变色性质.进一步对化合物4a在不同溶液中的动力学性质,以及在PMMA膜和PVB膜中的热消色动力学性质进行了研究,拟合计算并比较了消色过程的动力学常数.最后,又将化合物4a和不含含氮杂环的螺吡喃母体进行比较,发现耐疲劳度有很大提高.     

卟啉-二芳基乙烯分子的合成及其无损读取性能

二噻吩乙烯是一类性能优良的有机光致变色化合物,在信息储存领域具有广阔的应用前景,本文以2-甲基噻吩、苯甲醛和吡咯为原料,经过多步反应合成了1-(2-甲基-3-噻吩基)-2-{2-甲基-5-{4-[4-(10,15,20-三苯基-5-卟啉基)苯基]氨基羰基苯基}-3-噻吩基}环戊烯(DTE-TPP),其结构经核磁共振波谱仪(NMR)、质谱(MS)和傅里叶变换红外光谱仪(FTIR)表征确认,通过紫外-可见光谱研究了化合物的光致变色性能、抗疲劳性,并辅以荧光光谱探究了化合物的无损读取功能。结果表明,该化合物在254和660 nm的光照射下,发生可逆的光致变色反应,重复光照8次后其紫外-可见光谱与初始谱图相比无明显差异,显示出良好的抗疲劳性;当激发光为520 nm时,开、闭环异构体有较高的荧光对比度,有望实现数据的无损读取。     

钨硅酸/有机胺改性的二氧化硅纳米复合薄膜的制备和光致变色性质

光致变色材料由于在信息显示、传感器、调光器件和高密度存储等领域中具有显著的应用前景而备受关注[1] .杂多酸是一类含有氧桥的无机多核配合物 ,可作为电子受体与有机给体形成电子给 -受配合物 ,该类配合物在光激发下可发生电子转移 ,并表现出光致变色性 [2 ,3] .文献 [4,5 ]已报道了以杂多酸为电子受体设计制备光致变色化合物 ,并研究了其在固态和溶液中的光致变色性 ,但由于粉末和溶液本身的局限性而限制了其应用 .本文首次报道了由溶胶 -凝胶法将钨硅酸 ( Si WA)引入到有机胺改性的二氧化硅 ( APS)网络 ,得到 Si WA/APS纳米复合薄…     

二噻吩乙烯基四氮杂卟啉锌配合物的光致变色性质及红外无损读取性质研究

采用“一步法”合成了2,3,7,8,12,13,17,18-八-(2′,4′,5′-三甲基-3′-噻吩)四氮杂卟啉锌配合物,并通过谱学及元素分析对化合物进行了表征。电子吸收光谱及核磁信号的改变表明该化合物在365和730 nm波长的光照射下发生了可逆的光致开、关环反应。通过红外吸收光谱表征了该光致变色二芳基乙烯衍生物在溶液中开、关环前后结构的变化,并采用理论化学计算方法研究了该化合物开、关环异构体的红外吸收振动特性。光致变色异构化过程可以通过红外吸收光谱的变化而识别。关环异构体在1 705 cm     

双二芳基乙烯配体构建的Ag (Ⅰ)配合物及多色光致变色性质

采用闭环态紫外最大吸收波长不同的2个二芳基乙烯:1,2-双(2'-甲基-5'-(4"-苯腈)-3'-噻吩)全氟环戊烯(L1)和顺-1,2-二氰基-1,2-双(2',4',5'-三甲基-3'-噻吩)乙烯(L2)为配体,以Ag(Ⅰ)为金属离子、具有强配位能力的CF_3COO~-为阴离子,合成了一个新的双组分光致变色Ag(Ⅰ)配合物1。通过红外光谱、核磁共振氢谱及质谱对其进行结构表征。以直接混合的双配体体系(L1+L2)为对照,用UV-Vis光谱法研究了配合物1在四氢呋喃(THF)溶液和聚甲基丙烯酸甲酯(PMMA)薄膜中的多色态光致变色性质。结果表明,银离子配位没有抑制而是调节了 2个配体的光致变色性质,经254、405 nm和大于550 nm波长光的不同组合照射,可选择性地使1中2个配体发生分步光异构化反应,成功实现了黄色、蓝色、红色和紫色4个色态的转变。     

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.     

姜黄素稀土大环配合物的光致变色性能研究

通过模板反应, 以姜黄素和二乙烯三胺为配体合成了一系列的双姜黄素缩双二乙烯三胺(L)稀土大环配合物. 并用核磁共振氢谱、红外光谱、热重-差热、摩尔电导和元素分析进行了表征. 确定配合物的组成为: [LnL(NO₃)₃]•4H₂O (Ln＝La, Ce, Pr, Nd, Sm, Eu, Dy). 研究了配合物在室温下的荧光性质, 结果表明配合物表现出相应姜黄素的特征发射. 实验表明配合物具有良好的光致变色性能, 并用稳态和时间相关荧光光谱对配合物溶液的光致变色行为进行了研究. 在光照下, 配合物分子中的配体结构由烯胺式变为亚胺式, 溶剂对配合物光致变色性质的影响也进行了探讨.     

新型含吡咯亚胺基辅助配体的金属铱（Ⅲ）配合物的合成、表征及发光性质

合成了一系列含有吡咯亚胺基为辅助配体的2-苯基吡啶铱配合物[(ppy)zIr(NAN)](ppy=2-苯基吡啶),通过1H NMR,MS,HRMS和元素分析对配合物结构进行了表征,并研究了合成配合物的反应条件、紫外吸收光谱、光致发光光谱及铱配合物荧光量子产率.结果表明,在无水乙酸钠、二氯甲烷溶液中,室温反应12 h可获得较高的产率.通过改变吡咯亚胺类配体中的取代基,该类配合物在507～606 nm之间具有不同的发光波长,实现了从绿光到红光的转变.所有的铱配合物在二氯甲烷溶液(空气中)表现出较高的量子效率(0.25～0.95).     

Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

IntroductionThe investigation of organic photochromic materials has increased considerably in recentyears because of their potential commercial application in several areas,such as high-densityoptical storage media,optical switching,etc.[1 ,2 ] .Though numerous organic photochromicmolecular systems or photoactive devices have been explored so far,those systems classifiedaccording to the photochromic structural units mainly belong to a small number of families:fulgides,spiropyrans and spiroxazi…     

Synthesis, crystal structure and characterization of photochromic 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene

A novel photochromic diarylethene, 1,2-bis{2-ethyl-5-[2-(1,3-dioxolane)]-3-thienyl}perfluorocyclopentene (BEDTP), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its photochromic and fluorescent properties were also investigated. The results showed that this compound exhibited reversible photochromism, changing from colorless to magenta after irradiation with UV light both in solution and in the crystalline phase. In hexane solution, the open-ring isomer of BEDTP exhibited relatively strong fluorescence at 400 nm when excited at 282 nm. The fluorescence intensity decreased along with the photochromism upon irradiation with 254 nm light and its closed-ring isomer showed almost no fluorescence.     

吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物的合成及性质

针对有机光致变色材料实际应用中存在的光量子产率低,抗疲劳性差,记录信息在读取后遭到破坏等瓶颈问题,本文以2-甲基噻吩为原料,经过卤代、傅克酰基化、Mc Murry环合和Suzuki偶联反应得到的1-(5-氯-2-甲基噻吩-3-基)-2-(5-吡啶基-2-甲基噻吩-3-基)-环戊烯与锰(Ⅱ)-四苯基卟啉反应合成了吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物,通过紫外可见(UV-Vis)吸收光谱研究了其光致变色性能和抗疲劳性,并结合荧光光谱对无损读取功能进行了探究。实验结果表明,该化合物具有良好的光致变色性能及优良的抗疲劳性,通过波长为254、490和550 nm的光调控可无损地实现信息的写-读-擦过程,该物质有望应用于二进制存储设备中。     

1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。     

Photochemical cycloaddition reactions of cyanoacetylene and dicyanoacetylene.

Photolysis of cyanoacetylene with 185- or 206-nm light yields 1,3,5-tricyanobenzene while 254-nm radiation yields a mixture of tetracyanocyclooctatetraenes, 1,2,4- and 1,3,5-tricyanobenzene. A polymer of cyanoacetylene is the major photoproduct. 1,3,5-Tricarbomethoxybenzene was the only photoproduct identified from the irradiation of methyl propiolate at 254 nm. Mono-, di-, and tricyanobenzenes are formed by irradiation of mixtures of acetylene and cyanoacetylene at 185, 206, and 254 nm along with trace amounts of cyclooctatetraenes. No photoadducts were detected on photolysis of mixtures of cyanoacetylene and CO or HCN. The tetracyanocyclooctatetraene structures were established by UV, MS, and NMR analyses. The 1H NMR of the product mixture exhibited a singlet at delta 7.028 consistent with either 1 or 2 and two singlets at delta 6.85 and 6.91 assigned to 3. Photolysis of mixtures of dicyanoacetylene and acetylene with either 185- or 206-nm light yielded 1,2-dicyanobenzene and (E,Z)-1-buten-3-yne-1,4-dicarbonitrile. These products were also obtained using 254-nm light along with a mixture of tetracyanocyclooctatetraenes. The same three singlets were observed in this product mixture as were observed in the tetracyanocyclooctatetraenes obtained from cyanoacetylene. From this observation it was concluded that the delta 7.02 signal is due to 2 and not 1. The photolysis of cyanoacetylene and dicyanoacetylene in the presence of ethylene with 185-nm light yields 1-cyanocylobutene and 1,2-dicyanocyclobutene, respectively. 2-Cyanobutadiene and 2,3-dicyanobutadiene are the photoproducts with 254-nm light. Reaction pathways are proposed to explain these findings.     

Excitation-wavelength-dependent fluorescent organohydrogel for dynamic information anti-counterfeiting

Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption, but are still limited to static information display. Therefore, it is urgent to develop new materials and encryption-decryption logic for improving the security level of secret information. In this study, an organohydrogel made up of poly(N,N-dimethylacrylamide) (pDMA) hydrogel network and polyoctadecyl methacrylate (pSMA) organogel network that copolymerized with two fluorophores, 6-acrylamidopicolinic acid moieties (6APA, fluorescent ligand) and spiropyran units (SPMA, photochromic monomer), was prepared by a two-step interpenetrating method. As UV light of 365 nm and 254 nm can both cleave C_spiro-O bonds of SPMA, and the green fluorescence of 6APA-Tb³⁺ can only be excited by 254 nm light, the organohydrogel displays yellow and red under the irradiation of 254 nm and 365 nm, respectively. In addition to wavelength selectivity, these two fluorophores are thermal-responsive, leading to the fluorescence variation of the organohydrogel during heating process. As a result, secret information loaded on the organohydrogel can be decrypted by the irradiation of UV light, and the authenticity of the information can be further identified by thermal stimulation. Our fluorescent organohydrogel can act as an effective anti-counterfeiting label to improve the information security and protect the information from being cracked.     

Structure and solid-state photochromic properties of two new compounds with pyrazolone-ring

Two new organic photochromic compounds based on pyrazolone were synthesized and further characterized by elemental analysis, MS, IR spectra, and ¹H NMR spectra. The photochromic properties and photochemical kinetics of them have been studied by UV absorption spectra under irradiation of 365 nm light. The photochromism of pyrazolone derivatives in the solid state has been so far explained only in terms of the light-induced change of absorption and their crystal structures, which is caused by the shift of the tautomeric equilibrium between the enol and keto forms. In this work, their IR spectra have been measured before and after irradiation. Based on the IR spectra and crystal structure analysis, a reasonable mechanism was proposed, the photochromic phenomenon may be due to the photoisomerization from enol-form to keto-form through proton transfer.     

Characterization of A New Organic Photochromic Compound

A new organic photochromic compound, 1-phenyl-3-methyl-4-(4-fluoro)-benzal-5-pyrazolone ethanyl-thiosemicarbazone (PM4FBP-ETSC) was found to undergo photochromic reactions in the solid state. Upon irradiation with 365nm light the white powder sample turned light yellow. The photochromic properties were characterized by the time-dependent UV-vis reflective spectra. The structure of PM4FBP-ETSC was determined by single crystal X-ray diffraction.     

Photochromic Properties of β-Cyclodextrin Dimer Linked by Dithienylethene

A fi-cyclodextrin dimer tethered by photoswitchable dithienylethene moieties was synthesized as a potentially tunable receptor. The dimer exhibits pronounced photochromic properties. Irradiation of the dimer in open form with UV light at 254 nm resulted in immediate photocyclization to the pink closed form; the colorless open form could be regenerated by irradiation with visible light of wavelength >460 nm. The reaction kinetics of the forward photoprocess were also studied. To investigate the binding ability of the dimer in open and closed forms, a fluorescence titration was performed. It was found that the stability constant for the binding of TSPP (meso-tetrakis (4-sulfonatophenyl)porphyrin) by the closed form of the dimer is a factor of 5 higher than that of the open form.