吡咯取代的俘精酸酐及俘精酰亚胺的光致变色反应研究

对6个吡咯取代的俘精酸酐和1个俘精酰亚胺的光致变色行为进行了研究,发现取代基的不同对它们的光致变色过程有显著的影响.稳态动力学分析表明,呈色体(7,7a-二氢吲哚衍生物,II)的光消色反应遵循一级动力学反应规律.取代基对光消色反应的速率常数有一定的影响,对于呈色体(II)而言,2-3-位上有取代基的化合物,其光开环反应的速率常数明显大于2-或3-位无取代基的化合物.对于俘精酸酐的光反应而言,其反应比较复杂,不符合简单的动力学级数.在呈色体(II)的2-或3-位引入给电子基团可以使7,7a-二氢吲哚衍生物的吸收光谱发生红移,化合物II7的最大吸收波长在乙腈中可达720nm.溶剂极性的增大,可以使是色体的吸收光谱发生显著的红移,而对俘精酸酐本身的吸收光谱影响甚微.     

1,2,5—三甲基吡咯—3—甲叉（异丙叉）—丁二酸酐的合成与晶体结构

近年来,在光致变色材料研究领域中,人们的注意力从无机材料转移到有机材料。O-杂环俘精酸酐衍生物就是其中一类,但N-杂环俘精酸酐还没有引起人们注意。N-杂环俘精酸酐也能象O-杂环俘精酸酐一样在紫外光照射下环合成双氢吲哚的衍生物,N的给电子能力比O强,因此其双氢吲哚衍生物的吸收波长会出现红移。O-杂环俘精酸酐存     

新的光致变色有机化合物——环系俘精酸酐类

应用光致变色有机化合物作为光信息贮存的材料,虽经国际上的深入研究,但至今仍难满意地实现愿望。这主要由于已知的光致变色有机物对热不稳定以及存在着不可逆的副反应,从而影响其使用性能。如果光致变色作用与分子中键的均裂或异裂所产生的淤离基,离子或偶极中间体有关,则很难使有色体保持热稳定性或避免不可逆副反应。近年来H.G.海勒等在俘精酸酐类光致变色化合物的研究中有了新的进展。他们证明了这个体系的有色体1,8a-二氢萘衍生物是由相应的俘精酸酐按伍     

(口恶)唑环取代的俘精酸酐的合成及其光致变色性能的研究

合成了含噁唑环的俘精酸酐,4-（5-甲基-2-对甲氧苯基-4-乙酰基嘿唑）乙叉（异丙叉）丁二酸酐,研究了该化合物在不同溶剂中的光致变色性能,进行了光成色和光消色过程的动力学研究,并考察了溶剂极性对该化合物吸收光谱的影响。稳态动力学分析结果表明,该化合物呈色体的光消色反应遵循一级动力学规律,俘精酸酐本身的光反应比较复杂,不符合简单的动力学级数。     

光致变色双呋喃俘精酸酐的合成及其在平行图象存储中的应用

通过两步Stobbe缩合反应合成了一种双杂环俘精酸酐化合物, E,E-3,4-二[1-(2,5-二甲基-3-呋喃基)乙叉]-3,4-二氢呋喃-2,5-二酮(双呋喃俘精酸酐). 通过X射线单晶衍射, 对目标产物的分子结构进行了研究, 结果表明在该化合物中, 2个反应中心的距离分别是0.3394和0.3406 nm, 有利于光环合反应. 研究了该化合物在不同溶剂中的光致变色性行为, 并对目标产物在平行图象光信息存储中的应用进行了探索.     

芳环取代的俘精酸酐的合成及光致变色反应研究

本文报道四个芳环取代的俘精酸酐:2-亚异丙基-3-[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF1); 2-亚异丁基-3-[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF2);2-亚异丙基-3-[1-(α-萘基)-亚乙基]-丁二酸酐(NF1); 2-亚异丙基-3-[1-(β-萘基)-亚乙基]-丁二酸酐(NF2)的合成及其光致变色性质。测定了它们在不同溶剂中光致变色前后的吸收光谱。利用纳秒级激光闪光光解技术研究了它们的光致变色过程, 并讨论了其光致变色机理。结果表明, 这类芳环取代的俘精酸酐的光致环合反应是经过激发单重态进行的快速过程。     

芳环取代的俘精酸酐的合成及光致变色反应研究

本文报道四个芳环取代的俘精酸酐:2-亚异丙基-3-[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF1);2-亚异丁基-3-1[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF2);2-亚异丙基-3-[1-(α-萘基)-亚乙基]-丁二酸酐(NF1);2-亚异丙基-3-[1-(β-萘基)-亚乙基]-丁二酸酐(NF2)的合成及其光致变色性质.测定了它们在不同溶剂中光致变色前后的吸收光谱.利用纳秒级激光闪光光解技术研究了它们的光致变色过程,并讨论了其光致变色机理.结果表明,这类芳环取代的俘精酸酐的光致环合反应是经过激发单重态进行的快速过程.     

有机光功能材料分子设计研究: I. 俘精酸酐类光致变色材料量 子化学研究

用AM1对呋喃基取代的六种俘精酸酐类分子开环体、闭环体基态与激发态的结构进行了优化,所得俘精酸酐1的开环体基态平衡几何结构与已有的实验结果一致。计算结果能较好地解释俘精酸酐的热稳定性和光致变色性能,对取代基对俘精酸酐结构的影响取得了一些新的认识。根据俘精酸酐1开环体上各碳原子的净电荷密度,讨论了它的^1^3CNMR波谱。     

有机光功能材料分子设计研究: I. 俘精酸酐类光致变色材料量 子化学研究

用AM1对呋喃基取代的六种俘精酸酐类分子开环体、闭环体基态与激发态的结构进行了优化,所得俘精酸酐1的开环体基态平衡几何结构与已有的实验结果一致。计算结果能较好地解释俘精酸酐的热稳定性和光致变色性能,对取代基对俘精酸酐结构的影响取得了一些新的认识。根据俘精酸酐1开环体上各碳原子的净电荷密度,讨论了它的^1^3CNMR波谱。     

有机光功能材料分子设计研究Ⅰ.俘精酸酐类光致变色材料量子化学研究

用AM1对呋喃基取代的六种俘精酸酐类分子开环体、闭环体基态与激发态的结构进行了优化,所得俘精酸酐1的开环体基态平衡几何结构与已有的实验结果一致.计算结果能较好地解释俘精酸酐的热稳定性和光致变色性能,对取代基对俘精酸酐结构的影响取得了一些新的认识.根据俘精酸酐1开环体上各碳原子的净电荷密度,讨论了它的~(13)CNMR波谱.     

Photochromic Properties of Pyrryl Fulgides

We evaluated the photochromic properties of pyrryl fulgides by means of comparing their quantum yields of photocoloring, thermal stabilities and fatigue resistances.     

Structure and photochromic transformations of fulgides of the indole series

Previously undescribed fulgides of the indole series, viz., (1-methyl-3-indolylmethylene)- and (1-methyl-3-indolylethylidene) (isopropylidene)succinic anhydride, were synthesized. A Z conformation for (1-methyl-3-indolylmethylene) (isopropylidene)succinic anhydride and an E configuration for (1-methyl-3-indolylethylidene)-(isopropylidene) succinic anhydride were established by electronic and PMR spectroscopy and x-ray diffraction analysis. The photochromic properties of fulgides were observed and investigated. A scheme of photoinduced and thermal transformations of fulgides that includes a step involving Z E isomerization in the excited state is proposed. An additional photoisomer was recorded by pulse photolysis and fluorescence.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 33–41, January, 1990.     

Structures and photochromic properties of fulgides based on naphtho[1,2-<Emphasis Type="Italic">b</Emphasis>]furan and benzo[<Emphasis Type="Italic">g</Emphasis>]indole

The novel heterocyclic fulgides, i.e. 3-isopropylidene-4-{1-[5-methoxy-1-(4-methoxy-phenyl)-2-methyl-1H-benzo[g]indol-3-yl]ethylidene}dihydrofuran-2,5-dione and 3-isopropylidene-4-[1-(1-benzyl-5-methoxy-2-methyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione, were prepared and isolated as E-isomers. Photochromism, E-configuration, and high resistance to photocoloration—photobleaching of solutions of these fulgides as well as 3-isopropylidene-4-[1-(5-methoxy-2-methylnaphtho[1,2-b]furan-3-yl)ethylidene]dihydro-furan-2,5-dione and 3-isopropylidene-4-[1-(5-methoxy-2-methyl-1-phenyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione synthesized previously were shown by X-ray diffraction analysis, ¹H NMR spectroscopy and electronic absorption spectroscopy. The novel fulgides show fluorescence and high thermal stability of photogenerated cyclic form. Repeated photo-coloration—photobleaching is accompanied by reversible photoinduced E—Z isomerization. Benzo[g]indolyl fulgides are characterized by the longer wavelength absorption of both original (E) and photoisomeric cyclic (C) forms as compared to naphthofuran fulgide.     

3-Hydroxybenzo[g]quinolones: dyes with red-shifted absorption and highly resolved dual emission

New derivatives of 3-hydroxyquinolone (3HQ) with a fused benzene ring (3-hydroxybenzo[g]quinolones) have been synthesized. They display a remarkable red shift of their absorption spectrum in comparison with other 3HQ analogs allowing their excitation by common He/Cd and Ar-ion lasers. As a result of their irreversible excited-state intramolecular proton transfer (ESIPT) reaction, they display a dual fluorescence in a series of solvents of varying polarities, starting from toluene to methanol. The dual emission of these dyes correlates well with solvent H-bond basicity, which is connected with the effect of this solvent property on the kinetics of the ESIPT reaction. In addition to their red-shifted absorption and fluorescence, these new derivatives show a larger separation of their two emission bands and a more appropriate range of their intensity ratio than the previously synthesized 3HQs. These properties allow an improved ratiometric evaluation of the local H-bond basicity of unknown environments, which will favor future applications of the new dyes in polymer and biological sciences.     

Synthesis and two-photon absorption of highly soluble three-branched fluorenylene-vinylene derivatives

Two new three-branched fluorenylene-vinylene derivatives were synthesized by triple Heck-type or Horner-Wadsworth-Emmons reactions. Their one-photon absorption and fluorescence as well as their two-photon absorption properties are reported. These compounds, which combine very high solubility in organic solvents, high fluorescence quantum yield and giant two-photon absorption cross-sections in the red-NIR region (up to 3660 GM, in the femtosecond regime) are promising candidates for both optical power limiting applications and two-photon laser scanning microscopy.     

Photochromic fulgides based on 1-methyl-2-formylindole

The reactions of 1-methyl-2-formylindole with the diethyl esters of alkyl- and phenylmethylene-substituted itaconic acids led to the production of photochromic fulgides, which formed deeply colored 5,8b-dihydrocarbazole derivatives during UV irradiation. It was found by PMR that the fulgides also undergo E,Z isomerization during UV irradiation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 907–910, July, 1989.     

Synthesis and spectroscopic properties of new 5-oxazolone derivatives containing an N-phenyl-aza-15-crown-5 moiety

Novel 5-oxazolone derivatives containing an N-phenyl-aza-15-crown-5 moiety were synthesized for the first time. The structures of the new derivatives were confirmed by ¹H NMR, ¹³C NMR and FT-IR. In addition, evaluation of the visible absorption and emission properties of the structures were carried out in eight different solvents. The products show intense visible absorption maxima in the range 467-524 nm, and fluoresced strongly, with emission maxima from 496 to 689 nm in all the solvents tested.     

Synthesis and properties of coumarin-derived organogelators

A new family of coumarin derivatives containing amide group with different alkyl chain lengths was synthesized and their properties as organogelators were evaluated. It was found that the organogelation abilities were not obviously affected by the alkyl spacer length of amide group. Helical morphologies formed either in nonpolar or high polar solvents by most of the gelators. Occurrence of reversible and stereoselective photodimerization of the gel formed by 4-(7′-coumarinoxy)-N-octadecylbutanamide (3a) in cyclohexane was confirmed by ¹H NMR, UV absorption, and fluorescence spectra. The photoreaction of the gel proceeded without any dissolution, but the drastic microscopic changes of gel morphologies accompanied with the irradiation were identified using SEM and AFM investigations.     

Fluorescent photochromic fulgides

2-Indolylfulgides with different substituents were synthesized using the Sobbe condensation. All of these new fulgides show excellent photochromic behavior, and in addition, for the first time, the colored form of these fulgides has the unusual property of emitting rather strong fluorescence at room temperature when exposed to visible light.     

Styrene-PEG (600) DMA Crosslinked Polymers for Absorption of Oil Derivatives

In this work, styrene (St) based crosslinked polymers were prepared for removal of oil derivatives from aqueous solutions. Polyethylene glycol (600) dimethacrylate (PEG (600) DMA) was used as crosslinker in synthesis of styrene based crosslinked polymers, for the first time. The polymers were characterized by FTIR, SEM, elemental analysis and solvent (toluene, chloroform and fuel-oil) absorption capacities. The effects of different reaction parameters like crosslinker type, diluents amount and the presence of pore forming agent on the absorption properties of polymers were investigated. The polymers synthesized by using PEG (600) DMA have higher solvent absorption capacity than that of synthesized by using conventional crosslinker. Furthermore, the polymers synthesized in the presence of good diluents have higher absorption capacities. The addition of pore forming agent into the reaction medium has also improved the absorption rate of polymers. The absorption capacity of polymers in different solvents is in order of chloroform > toluene > fuel-oil. It was seen that oil derivatives can be removed efficiently from water by the St-PEG (600) DMA polymers.