用循环伏安法研究烷氧基聚紫精的电氧化还原性能

利用循环伏安法研究了烷氧基聚紫精的电氧化还原性能，测定了它们的两步还原电位、峰电流和表现扩散系统（Ｄ），结果表明：Ｄ随着ＰＡｏＶ结构中所含醚键的增加而减小；并对第一步还原反应的可逆性进行了研究，发现第一步还原反应的可逆性优于第二步还原反应，同时证明电极反应是由扩散步骤控制的；ＰＡｏＶ具有良好的抗电疲劳性能；并研究了体系ｐＨ值和扫描范围对ＰＡｏＶ的电氧化还原性能的影响。     

苯氧基萘并萘醌衍生物的合成与光致变色性能研究

设计合成了16个新的具有不同迁移基团、不同取代基及双苯氧基萘的苯氧基并萘醌化合物; 通过红外光谱、核磁共振、质谱等方法对其结构进行了表征; 利用紫外-可见光谱研究化合物的光致变色性, 结果表明, 化合物的结构影响其变色性能, 当迁移基团为芳香基时, 其变色性较好; 主链醌环上有取代基时, 化合物成色体最大吸收波长红移; 双苯氧基萘并萘醌化合物较相应的单化合物有较大的摩尔吸光系数; 随着苯基上取代基增大, 其成色速率常数变小.     

新型准轮烷的合成及性质研究——丁烷基紫精与葫芦[6]脲的超分子自组装

通过葫芦[6]脲(CB[6])与丁烷基紫精(BV)在水溶液中于室温下进行超分子自组装, 得到一种新型的准轮烷(BVCB), 并通过¹H NMR, IR, 质谱, 元素分析对其结构进行了表征, 证实CB[6]位于BV的脂肪链上通过非共价键与BV结合, 并且 CB[6]与BV的结合摩尔比为2∶1; 通过热重分析(TGA)、紫外-可见吸收(UV-vis)和化学还原等方法对其性质进行了研究, 证实了BVCB比BV有更高的热稳定性、UV-vis吸收和更强的氧化能力; 盐效应表明 NaI是BVCB优良的沉淀剂; 环境扫描电镜(ESEM)证实BVCB比BV具有较强的刚性和较差的结晶能力.     

含氯化铜的紫精/聚合物薄膜制备及光致变色性能研究

将氯化铜加入到紫精/聚乙烯吡咯烷酮中,制得了一种可快速褪色、光疲劳性能优异的紫精/聚合物光致变色薄膜,测试了该薄膜的变色性能、褪色性能及光疲劳性能.结果表明,氯化铜的加入使薄膜初次紫外光照时的颜色变浅,但加快了薄膜褪色;当氯化铜与紫精摩尔比为1:1、60℃褪色时,薄膜光照后在610 nm处吸光度的半衰期为9 min,而不合氯化铜的薄膜为54 min,氯化铜含量越高,半衰期越短.含有氯化铜的薄膜,随变色/褪色循环次数增加,光照后的显色加深,氯化铜含量越高,颜色增加的程度越大.该功能薄膜可用于信息存储、太阳镜及智能窗等方面.     

丙烯酰氧基螺噁嗪衍生物的合成和光致变色性

合成了2种未见文献报道的9′-丙烯酰氧基吲哚啉螺萘并噁嗪衍生物(Ⅲa、Ⅲb),通过核磁共振氢谱、红外光谱确认了其结构.研究了在Zn(Ⅱ)螯合情况下,Ⅲa的紫外-可见吸收光谱,Zn(Ⅱ)螯合可以明显提高其开环体的热稳定性.     

Acid/Alkali Gated Photochromism of Diarylethenes with Quinoline Derivatives

Three new diarylethenes 1 – 3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons under UV/Vis light irradiation in chloroform solution. It was found that 1 – 3 had well photoisomerization upon UV/Vis light irradiation in neutral chloroform solution. Addition of acid to the solution of the ring‐opening isomers of 1 – 3 produced 1oa – 3oa , which performed reversible photochromic behavior under UV/Vis light irradiation and reversed back to 1 – 3 under neutralizing with adding lewis base. However, addtion of base to neutral soluton of the ring‐opening isomers of 1 – 3 produced 1ob – 3ob , which could not change to the deprotonated ring‐closing isomers under UV light irradiation.     

紫罗碱衍生物分子结的电学性质理论研究

本文基于密度泛函(DFT)结合非平衡格林函数(NEGF)的方法,以具有氧化还原中心的紫罗碱衍生物(N,N'-bis(4-thioalkyl)-4,4'-bipyridinium,HS-4V4-SH)功能分子构造Au(111)/S-4V4-S/Au(111)分子结,详细分析了分子在三种价态V、V+和V2+下的电学性质与分...     

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     

侧基含偶氮苯生色团的短梗霉多糖的制备及光致变色性

利用4-(4-硝基苯偶氮)-1-萘酚的丙烯酸酯与短梗霉多糖进行接枝共聚,制备了侧基含偶氮苯生色团的短梗霉多糖聚合物,并用红外光谱、扫描电镜、X射线衍射、热重分析等手段对聚合物进行了表征.用紫外光谱研究了聚合物的光致变色性,结果表明聚合物具有良好的热稳定性和光致变色性.     

萘氧基萘并萘醌的合成和光致变色性质

萘氧基萘并萘醌的合成和光致变色性质方政，杨志范，王淑芝，徐素贤，方天如，王佛松（吉林工学院化工系长春）（中国科学院长春应用化学研究所长春１３００２２）关键词萘氧基萘并萘醌，合成，光致变色苯氧基萘并萘醌类光致变色材料具有耐疲劳，室温下几乎无热消失反应，...     

Interfacial Behaviors of Azocalixarene Derivatives at the Air/Water Interface and Photochromism in the Langmuir-Blodgett Films

The azocalixarenes is a novel chromogenic compound and their spectra properties have been reported. A number of them have been applied as selective ionophores in extractive process1 or as selective ligands in ion selective electrodes and optical sensors based on spectra changes2. Some amphiphilic azocalixarene derivatives with hydrophobic long alkyl chains were synthesized and their interfacial behaviors at the air / water interface have also been investigated3. However, the photochromism of t…     

Interfacial Self‐Assembly of Closely Packed Nanoparticle Arrays of Silica@Multiporphyrin Hybrids as Light‐Sensitizers for Dye Degradation and Viologen Photochromism

Light‐sensitizer functionalized organic–inorganic hybrid materials have attracted much attention owing to their potential applications in the fields of optoelectronics, heterogeneous catalysis, sensors, and nanotechnology. Here, an interfacial self‐assembly of zero‐dimensional (0D) silica@multiporphyrin array nanohybrids and their 3D Langmuir–Blodgett (LB) films is reported. Photoactive tetrapyridylporphyrin (TPyP) was first assembled on the silica nanoparticles’ surfaces via silane, substitution, and coordination reactions to produce nanoSiO₂@(Pd‐TPyP)_n hybrids. Then, the Cd²⁺‐nanoSiO₂@(Pd‐TPyP)_n monolayers and LB films were constructed on the CdCl₂ subphase surface. These monolayers and LB films displayed stronger stability, as well as more uniform and closely packed nanoparticle arrays compared with those prepared on the pure water surface, owing to the formation of strong network‐like Pd‐ and Cd‐TPyP coordination units, which significantly enhanced the nanoparticles’ interaction. Further, compared with that of the 0D nanoSiO₂@(Pd‐TPyP)_n hybrids, the degradation efficiency was nearly 20 times higher when the hybrids’ LB films were used as light‐sensitizers for the photocatalytic degradation of RhB. Finally, flexible photochromic devices were constructed by using the LB films sandwiched between two electrodes, which displayed a reversible photoinduced redox reaction of viologen together with a color change process. Because TPyP was strongly immobilized on the nanoparticles’ surfaces and the particles were connected through the Py‐Pd²⁺‐Py and Py‐Cd²⁺‐Py coordination units with the 3D network‐like architecture, the present nanohybrids and LB films had good stability and reusability.     

多钼酸盐–柠檬酸复合膜的多色光致变色

制备了多钼酸盐–柠檬酸光致变色复合膜，紫外光照后发现不同摩尔比的复合膜呈现不同的颜色。当摩尔比为1.0，0.3和0.2时，变色后的薄膜分别显深蓝色，深黄褐色和淡海绿色。通过对薄膜的拉曼光谱分析证实呈现不同的颜色是由于在变色后的膜中生成了不同的物种。柠檬酸在光致变色过程中起着重要的作用, 在紫外光的照射下它作为空穴的捕获剂, 抑制了光生电子和空穴的复合, 使多钼酸盐呈现紫外光致变色现象。     

基于环糊精二聚体与紫精聚合物的包结作用制备超分子水凝胶

制备了对苯二甲酸连接的环糊精二聚体(α,α-CD Dimer)及紫精聚合物(VP), 利用α,α-CD Dimer与VP之间的主客体识别作用构筑了一种超分子水凝胶. ¹H NMR测定结果表明α,α-CD Dimer和VP的主客体相互作用是通过α-CD空腔和VP形成包结络合物进行的. 环糊精二聚体α,α-CD Dimer和聚合物VP凝胶体系的构筑受环糊精二聚体类型的影响, 同时该超分子水凝胶对有竞争作用的客体分子表现出响应性, 该超分子水凝胶在竞争性客体分子存在的条件下, 可发生小分子诱导的凝胶与溶胶转化行为. 此外, 该凝胶体系还具有良好的热稳定性.     

烷基紫精化合物的电氧化还原行为

用微分脉冲极谱法研究了烷基紫精及聚紫精的电氧化还原行为。紫精的烷基影响紫精化合物的还原电位及其还原产物在电位及其还极上的成膜性能。与低分子烷基紫精相比，烷基聚紫精的第一还原电位Ｅ１较正，两步还原反应的电位间隔△Ｅ较大，而且两步还原反应均有良好的可逆性。支持电解质的卤素离子对紫精化合物还原电位有影响，其影响能力的顺序为：Ｉ＾－＞Ｂｒ＾－＞Ｃｌ＾－＞Ｆ＾－。     

Photochromism and the spectral properties of bispiroanthro-bis-oxazine

The spectral and photochromic properties of bispiroanthro-bis-oxazine (bis-SAO) in toluene, DMF, and polystyrene films were investigated in the 77–300 K interval. It is shown that the long-wave part of the absorption spectrum of the starting form of the molecule is formed by three-electron transitions localized in the anthro-bis-oxazine fragment. The directions of the oscillators of these transitions relative to the nuclear. backbone of the molecule are proposed on the basis of luminescence polarization data. It is proposed that the photochromic properties of the solutions are determined by the existence of bis-SAO molecules in dimer form.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Institute of Solid State and Semiconductor Physics, Academy of Sciences of Belarus, 210023 Vitebsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2718–2725, December, 1992.     

Photochromism of Peroxotungstic Acid/PVP Nanocomposite Obtained by Sol-Gel Method

Peroxotungstic acid (PTA)/PVP composite film was prepared via sol-gel method. TEM revealed that the composite films consist of peroxotungstic acid nano-grains embedded in amorphous PVP matrix. The samples were observed to exhibit reversible photochromic effect when irradiated with solar light. The iodometric titration and FT-IR spectra indicated the presence of peroxo groups (W–O–O–W) incorporated into PTA structure. EPR measurement revealed the presence of unpaired paramagnetic electrons in PTA/PVP nanocomposite gel. The UV-Vis-Nir transmittance spectra and EPR spectroscopy of sample indicate that the photochromic behaviour is due to the photo-excitation of the unpaired electrons at W–O octahedral sites of peroxotungstic acid.     

2-芳氧基-1,8-邻苯二甲酰基萘的合成及光致变色性

合成了3种2-芳氧基-1,8-邻苯二甲酰基萘类光致变色化合物,通过核磁共振谱、红外光谱、质谱和元素分析确定了结构.对产物进行了荧光光谱测定,3种光致变色化合物的荧光强度和Stoke位移都较大.用紫外-可见分光光度计对其在丙酮溶液中的光致变色行为进行了测定,3种光致变色化合物在300-600 nm范围内都具有一定的光致变色性能和较大的吸光系数.     

磺酸功能化的离子液体型多金属氧酸盐的光色性能

发现磺酸功能化离子液体型多金属氧酸盐(IL-POM)具有可逆光色性质,并在紫外光激发下,详细考察了[PyPS]_nH_3-nPW₁₂(n=1,3)(PyPs:吡啶丙磺酸盐)、[PyPS]₄SiW₁₂、[TEAPS]₃PW₁₂(TEAPS:3-(三乙胺基)丙磺酸盐)等样品的光致变色行为。 结果表明,磺酸化的IL-POM是一类弱的电荷转移多金属氧酸盐,但在紫外光激发下有机阳离子和POM阴离子间可以发生电子相互作用,实现W⁶⁺→W⁵⁺的还原,并形成稳定的电荷转移复合物,导致样品显色。 钨磷酸盐的光色性大大强于钨硅酸盐,且空气中避光放置可以消色。 但样品容易疲劳,着色-褪色重复性不好。 对光色机理的研究显示,有机阳离子中的-SO₃H基团作为电子供体参与了变色过程。 揭示了磺酸基团的电子供体作用,为设计电荷转移多金属氧酸盐和POM基光色材料提供了新的思路。     

一种新的含吡唑啉酮氨基硫脲化合物的晶体结构及其光致变色性质

A new photochromic organic compound of thiosemicarbazone, 4-（p-bromo-α-methylaminothiocarbonyl hydrazonobenzal）-2,5-dihydro-3-mcthyl-5-oxo-1-phcnyl pyrazolc, was synthesized and characterized by elemental analyses, IR, ^1H NMR spectra, and X-ray single-crystal diffraction analysis. The compound exhibited an interesting photochromism in the solid state when irradiated by ultraviolet light at 365 nm. The photochromic kinetics was studied by the time-dependent powder UV-Vis reflectance spectra. The intcrmolecular and intramolecular hydrogcn-bonding interactions may be responsible for the photochromic phenomenon.