Schiff碱N,N’-双水杨醛缩-1,6-己二胺的光致变色光谱研究

用稳态和时间相关荧光光谱、紫外 -可见吸收光谱和傅立叶变换红外光谱等方法研究了 Schiff碱N ,N -双水杨醛缩 -1 ,6-己二胺 ( BSH)的光致变色行为 .确定了光致变色的产物为双质子转移的酮式结构 .     

Schiff碱N,N-双水杨醛缩-1,6-己二胺的光致变色光谱研究

用稳态和时间相关荧光光谱、紫外-可见吸收光谱和傅立叶变换红外光谱等方法研究了Schiff碱N,N-双水杨醛缩-1,6-己二胺(BSH)的光致变色行为. 确定了光致变色的产物为双质子转移的酮式结构.     

N,N,N′,N′-对四甲基苯二胺光致电子转移变色体系的研究

研究了由N,N,N′,N′-对四甲基苯二胺(TMPD)/电子受体组成的光致电子转移变色体系,及其在溶液中和高分子膜中的光反应和热稳定性。实验结果表明这类光致变色体系具有较高速度的光响应能力。在不同芳胺/碘鎓盐(DPIOC)组成的体系中,可观察到电子转移速度随芳胺的氧化还原电位下降而增加:TMPD>N,N-二甲基苯胺>三苯胺>二苯胺。光反应速度和反应物浓度具有一定指数关系,分别为0.66(TMPD)和0.16(二苯基碘铕盐)。在TMPD/卤代烃(RX)组成的体系中,发现卤代烃的C—X键较弱时,体系的光致生色反应速度较快。显然,这是由于反应中间产物(RX^-)的分解有利于减少电子逆转移反应的缘故。在聚甲基丙烯酸甲酯高分子膜中的光致生色反应效率显著地高于溶液中的反应效率,并能获得较高的光密度。热稳定性结果表明,温度对色稳定性有显著影响,每经过一次生色/褪色循环,体系的发色能力下降一半左右。     

有机铵十聚钨酸盐在溶液中的光致变色性质研究

有机铵十聚钨酸盐具有显著的光致变色性质,电子自旋共振研究表明光致变色是由于光照过程中有五价钨生成,发生了光还原反应。本文研究了二异丙胺和六氢吡啶十钨酸盐(分别简写为DIAW_(10)和PIPDW_(10)在溶液中的光致变色性质,考察了水、乙腈、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)对光致变色性质的影响,对比研究了四丁基铵盐(NBuW_(10))的情况,还测定了不同光照时间下W(V)浓度,可见吸收光谱和循环伏安,提出了光致变色性质与体系中所含活泼氢的定量关系,初步揭示有机铵十聚钨酸盐光致变色的本质。     

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.     

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.     

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。     

信息动态

有机光电功能材料作为一种新型功能材料,已应用于高科技领域和民用领域,故借2016年11月召开“2016年国际光致变色会议”之机出版主题专辑,内容主要涉及光致变色和荧光探针领域,希望可以为相关领域的研究人员提供一个展示成果的平台,推动包括光致变色等有机光电功能材料研究工作的深入开展. 此次国际光致变色会议主题之一的有机光致变色材料是光化学研究的重要内容之一,其种类繁多,反应机理也不尽相同,如何根据光物理和光化学原理设计出新型低背景颜色、抗疲劳性强、易于调控的分子,是有机光致变色材料研究的基础.本专辑中的综述文章介绍了不同体系的光致变色材料,包括萘并吡喃光致变色荧光体系(东北师范大学王广等)和二芳烯类光致变色体系(南昌大学蒲守智等)在分子开关器件的应用,还介绍了有机分子三重激发态的调控与应用(大连理工大学赵建章等),并特别感谢赵建章老师精心设计了专刊封面.这些光致变色体系和发光体系都是近年来国内外研究的重点工作.     

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.     

12-钼磷酸与聚乙烯醇固容体的光致变色及其稳定性

以ESR,XPS,IR和UV-vis等手段,研究12-钼磷酸与聚乙烯醇黄色固容体的光致变色及其稳定性。由测试结果得知,该固容体的光致变蓝色是因其在紫外光照射下的光化学反应产物多价钼(VI,V,IV)配合物呈蓝色,而另一种产物带部分羰基的聚乙烯醇为无色所致。随着它们的生成,后者产物因具有螺旋状结构能与前者产物发生包合作用,从而提高光致变色的稳定性。     

铕-N,N-二(N-亚甲基琥珀酰亚胺)甘氨酸-1,10-二氮杂菲三元配合物的光致变色

合成了N,N-二(N-亚甲基琥珀酰亚胺)甘氨酸,并以元素分析、IR、¹HNMR和质谱进行表征.实验中发现铕(Ⅲ)与N,N-二(N-亚甲基琥珀酰亚胺)甘氨酸和1,10-二氮杂菲形成的配合物具有光致变色的性质.在铕变色物种里,铕离子与N,N-二(N-亚甲基琥珀酰亚胺)甘氨酸中的羧基,1,10-二氮杂菲中的氮原子相结合,同时也可能与水分子和羟基基团结合.     

A Novel Route to Synthesize N,N‐Dimethyl Arylmethylamines from Aryl Aldehydes,Hexamethylenetetramine and Hydrogen†

Developing simple and green routes to access valuable chemicals is of significance. Herein, we present a green and novel route to synthesize N,N‐dimethyl arylmethylamines (DAMAs) from hexamethylenetetramine (HMTA) and aryl aldehydes in the presence of hydrogen, and a series of DAMAs can be obtained in good yields. This approach opens the precedent for HMTA as N,N‐dimethylamine source to synthesize chemicals with N,N‐dimethylamine group, which has promising applications for N‐containing chemicals synthesis.     

1,4-双(4′-N,N-二甲基氨基苯乙烯基)萘的合成及荧光性质

利用Wittig反应合成了一个以萘为π-Center的对称型“D-π-D”有机绿色发光化合物1,4 双(4′-N,N-二甲基氨基苯乙烯基)萘(BDASN),并测试了其在不同环境中的光谱性质.在378nm激发波长的激发下,BDASN显示出很强的荧光发射峰,峰位在521nm(CH₂Cl₂).随着溶剂极性增大,最大发射波长红移且荧光强度降低,与“D-π-A”分子具有相似的分子内电荷转移(TICT)行为.在β-环糊精(β-CD)中BDASN的绿色发光带被猝灭,同时在450nm附近蓝发光带的荧光强度骤增.     

Synthesis and characterization of yellow water-borne polyurethane using a diol colorant as extender

<正>A novel and facile method toward a series of yellow water-borne polyurethane was developed by using an intrinsically colored diol in this paper.The yellow aqueous dispersion PCLD-HENA-PU was synthesized based on isophorone diisocyanate(IPDI), polycaprolactonediol(PCLD) and 2,2-dimethylol propionic acid(DMPA) using a yellow diol N,N-bis(2-hydroxyethyl)-4-nitroaniline (HENA) as a chain extender.Due to the complete reaction of OH group in colorant HENA with NCO group in diisocyanate,a series of stable yellow polyurethanes could be obtained conveniently and easily.The structure of PCLD-HENA-PUs was confirmed by means of Fourier transform infrared spectroscopy.The UV-visible absorption analysis showed a blue shift effect of about 7 nm when HENA was blocked into polyurethane chain.The absorption intensity of PCLD-HENA-PUs increased with increasing HENA content.It was found that the tensile strength enhanced from 8.6 to 19.6 MPa with HENA content increased from 0 to 18.0%,while the extensibility decreased from 449 to 300%.The thermal gravimetric analysis presented that the initial decompose temperature began from about 250℃,and had a little increase with increasing the HENA content.     

Visual detection of anions by a novel isothiourea-based chromophore.

S-Methyl-N-methyl-N'-(4-(N",N"-dimethylamino)phenyl)isothiourea, a novel isothiourea-based chromoionophore for anions, was synthesized. The reactivity for several anions was estimated by a visual method and UV-vis spectroscopy. By the addition of acetate ion, a blue shift in the absorption spectrum was observed in CHCl3, and the solvent color changed from yellow to colorless. These changes indicated that bound acetate ion interfered with the intramolecular charge transfer from the nitrogen atom of the diethylamino group to the isothiourea moiety. The addition of chloride ion caused a red shift of the chromophore and solvent color remained yellow. By the addition of dihydrogenphosphate ion, the precipitate was formed immediately. These anion-dependent natures of the chromoionophore allowed us to detect acetate and phosphate ions easily.     

自由基C59N及双体(C59N)2的理论研究

用INDO系列方法对自由基C59N及双体(C59N)2进行了理论研究,结果表明: N的掺入使C60笼发生畸变, N向笼外突出, 碳氮6-6键上的C自旋密度较大, 两C59N自由基在这个碳上以C-C单键连接形成双体为C2h, C2v对称性。其中C2v构型更稳定, 且N与附近的三个碳均以单键连接。理论计算的电子光谱与实验吻合较好。(C59N)2易分解为单体C59N。     

一个由吡嗪-2,3-二甲酸和咪唑构筑的锌配位聚合物的水热合成、晶体结构及荧光性质(英文)

A metal-organic coordination polymer [Zn2(pzdc)(im)3]n(H2pzdc=pyrazine-2,3-dicarboxylic acid,im= imidazole) 1 has been hydrothermally synthesized and characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction.Pale yellow crystals crystallize in the monoclinic system,space group P21/c,a=1.364 87(15) nm,b=1.389 43(15) nm,c=0.956 89(10) nm,β=102.354(2)°,V=1.772 6(3) nm3,C15H12N8O4Zn2,Mr=499.07,Dc=1.870 g·cm-3,F(000)=1 000,Z=4,μ(Mo Kα)=2.750 mm-1,the final R=0.032 2 and wR=0.087 8 for 3 208 observed reflections(I2σ(I)).1 shows green photoluminescent property at room temperature.     

Synthesis and Photoluminescence of Eu-doped ZnO Nanosheets

Eu-doped ZnO nanosheets were synthesized successfully by means of the hydrothermal method. The X-ray diffraction(XRD) pattern shows that the sample is a single phase with the ZnO-like wurtzite structure. And the X-ray photoelectron spectrum suggests that there are Eu3+ ions in the matrix of the sample. Eu3+-related red emissions resulted from energy transfer were observed for the nanosheets under UV laser excitation. The UV, green and yellow emissions were also seen in the photoluminescence spectra.     

Mixed lithium amide-lithium halide compounds: unusual halide-deficient amido metal anionic crowns

Molecular salt cellars: The addition of substoichiometric quantities of lithium halides to the lithium hexamethyldisilazide was studied. Surprisingly, a novel class of mixed amido-halide macrocyclic complexes, namely metal anionic crowns (MACs) was revealed (see picture: Li?pink, N?yellow, Cl?green, Si?orange, C?black).     

A 15N NMR investigation of a series of benzotriazinones and related antitumour heterocycles

A series of 3‐substituted 1,2,3‐benzotriazin‐4‐ones, 1 and 2, were synthesized by standard methods and the ¹⁵N NMR spectra were recorded. All spectra were obtained using the natural abundance of the nitrogen‐15 isotope. The chemical shifts appear in the normal range for N‐1, N‐2 and N‐3 of the triazine ring, and also correlate with the chemical shifts in the spectra of the imidazolotriazinone, 4, and the imidazolotetrazinone, 5. Significantly, the spectra of 1a, 2 and 4, recorded with full NOE, show inversion of the singlet assigned to N‐3, demonstrating that these compounds exist in the tautomeric form shown. The structure of the 4‐iminobenzotriazinone (3) was confirmed by this ¹⁵N NMR analysis. The spectrum shows a signal for the NH‐bearing imino‐nitrogen atom, which is an inverted singlet in the NOE spectrum, whereas the signal from the N‐3 atom of 3 is not inverted in the NOE spectrum. Copyright © 2002 John Wiley & Sons, Ltd.