螺吡喃逆向变色光量子产率测定及其光致变色特性研究

研究了1'-十八烷基-3',3',-二甲基-6,8-二硝基螺[2H-1-苯并吡喃-2,2'-吲哚啉]的逆向光致变色特性,通过吸收光谱测定了其在不同溶剂中可见光照后无色体(SP)的开环生色速率常数及在甲醇中有色体(MC)光照关环的光量子产率,发现溶剂的极性对开环有色体(MC)的吸收光谱影响较大,但对无色体的开环速率常数的影响相对较小。利用¹HNMR分析了SP和MC的结构,证实了MC处于反式构型。     

两种新型阳离子吲哚啉螺吡喃的合成、表征和光致变色性质的研究

螺吡喃是一类重要的光致变色化合物．螺吡喃的正向光致变色是指在紫外光照下,螺吡喃分子的Ｃ—Ｏ键异裂,由闭环无色体（ＳＰ）可逆地变成开环有色体（ＭＣ）．所形成的有色体可以在暗条件下热致褪色或在可见光照下褪成无色体（示意图１）．它的逆向光致变色是指某一类螺...     

光致变色螺吡喃化合物的合成及光致变色性质测定

光致变色螺吡喃化合物的合成及光致变色性质测定赵福群，周金渭，张复实，唐应武，宋心琦（清华大学化学系，北京１０００８４）目前本科教学中涉及光化学的实验很少，学生对这方面的理性知识和感性知识知之甚少，而光化学是目前一个非常活跃的研究领域。有鉴于此，我们结...     

十八烷基取代吲哚啉螺吡喃衍生物的合成及光谱性质

螺吡喃类化台物是一种重要的光响应分子,它在光信息存储技术中作为光盘材料具有广阔的应用前景。这类化合物在不同介质中的光谱、光电和光致变色性质引起了众多科学家的兴趣,并且已有大量研究工作报道。近年来,光致变色固体膜,特别是光致变色化合物的LB膜和超分子膜的特性引起了广泛的关注。因为在这种状态下,化合物分子具     

一种含螺吡喃和肉桂酸酯双光功能基团的光致变色染料的合成与性能

合成了一种含有光致聚合肉桂酸酯基团的新型光致变色螺吡喃染料,研究其与普通螺吡喃染料在不同高分子材料中的光致变色和热退色过程(PMMA和PVCi).通过UV-Vis光谱、NMR谱和IR光谱研究了新型染料中的肉桂酸酯基团的光致聚合过程,考察了其对螺吡喃结构的光致变色显色体热稳定性的影响.     

螺吡喃衍生物的光致变色过程的时间分辨光谱

在环已烷和乙腈的稀溶液中测定了1,3,3-三甲基-6′-硝基螺[吲哚啉-2,2′[2H]-苯并吡喃]光致变色过程的纳秒、微秒激光闪光光解光谱。实验结果表明:闭环体A的C—O键异裂发生在闭环体的激发单线态~1A~*而成为顺式结构单线态~1X~*(螺C—O键已断开,但仍保持闭环体的结构)和~3X~*(~1X~*系间窜跃)。中间产物~1X~*在纳秒级时间内很快生成CT(charge-separation twist state),CT吸收峰位置(580nm)基本上不受溶剂极性的影响,这说明其不是反式、两性离子结构的部花菁B。三线态~3X~*在氮气饱和溶液中的消减途径有2个,一是经基态X生成部花菁B,又因~3X~*的分子结构更接近闭环体A,其同时释放能量回到基态闭环体A。氧气饱和的溶液中,三线态~3X~*被猝灭成为X,其主要产物是部花菁B。此时反式两性离子结构的部花菁B生成速度变快、吸收强度变大。产物CT在环己烷溶液中和部花菁B共同存在,而在极性溶剂乙腈中,其最后生成了稳定的两性离子结构体部花菁B。     

一种支链含有螺吡喃和查尔酮双光功能基团的复合高分子材料光致变色性能研究

合成了两种支链含有光致变色的螺吡喃结构的复合高分子材料, 观察了光激发下材料的光致变色动力学过程. 一种高分子材料为丙烯酸甲脂(MMA)和丙烯酸-螺吡喃单体(MMA-Spiropyran)的共聚物, 另一种是丙烯酸-查尔酮单体(MMA-Chalcone)和丙烯酸-螺吡喃单体的共聚物. 利用紫外-可见光谱仪对合成的复合高分子材料的光敏性能进行了考察, 从研究中发现, 材料的光致聚合过程对其光致变色显色体稳定性的影响.     

冠醚螺吡喃化合物的合成和光致变色性质

合成了四个新的6位带不同取代基的含冠醚结构单元吲哚啉螺苯并吡喃化合物(5a-5d),研究了其光致变色性质和离子诱导光致变色作用及取代基的影响。结果表明冠醚能稳定螺吡喃开环形式,碱金属离子对冠醚螺吡喃的生色有诱导作用;6位为吸电子基团时,螺吡喃开环形式的稳定性增加,而6位为推电子基团时,螺吡喃开环形式的稳定性降低。另外,就稳定螺吡喃开环体的作用来说,吲哚啉环上的取代基效应和苯并吡喃环上的正好相反。     

光诱导有机化合物异构化反应的研究——Ⅹ. 吲哚啉螺吡喃瞬态吸收光谱的研究

研究了1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(2-溴-4-硝基-苯并)吡喃, 1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(4-硝基-苯并)吡喃, 1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(2,4-二硝基-苯并)吡喃及1-正-辛基-3,3-二甲基-吲哚啉-2,2′螺-5′6′-(2-氯-4-硝基-苯并)吡喃在环已烷和甲苯溶液中光致开环过程的瞬态吸收光谱。观察到具有较长寿命的中间体及聚集体的存在。初步提出异构化反应过程的机制中既包含有三重态过程, 也有单重态参与。     

新型螺吡喃化合物的合成及应用研究

设计合成了几种新型螺吡喃化合物(SP), 采用¹H NMR, IR 和MS 对其结构进行表征. 研究了目标产物的光致变色性能及其影响因素, 并对SP1 在高分子材料领域的应用作了初步研究. 结果表明: 苯并吡喃环连有强吸电子基时, 最大吸收峰红移; 1 位N原子上连有柔性长链基团时, 热褪色速率较慢; 采用紫外光照射目标产物不同时间, SP1 表现出较好的抗光疲劳性. 分别以SP1 为接枝组分和共混组分制备两种高分子材料SP-g-hPMMA 和SP-m-PMMA, 通过紫外光辐照动力学研究表明, SP-g-hPMMA 和SP-m-PMMA 均表现出比SP1 优异的光致变色性能, 且不影响PMMA 的机械性能. SP1 有望用于高分子光致变色材料领域.     

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.     

吲哚啉螺吡喃热致变色平衡常数的热测定法

报导了一种吲哚啉螺吡喃（SP）在丙酮溶液中热致变色平衡常数的新测定方法．通过分别检测紫外光照射SP后生成有色体的褪色过程和避光条件下其开环异构体与Cu（Ⅱ）的配合物形成过程，求得闭环无色体的开环速度常数kf和开环有色体的闭环褪色速度常数（kr）分别为4．94×10－4s－1和9．8×10－2s－1．利用Ke＝kf／kr，可求得Ke为5．0×10－3．此方法有助于解决Flannery等人方法中对不同溶剂ε估值所带来误差的问题．     

Synthesis of New Spiropyrans With a Polyaromatic or Heteroaromatic Pendant and Their Photochromic Behaviors

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Fabrication of Patterned Images in Photochromic Organic Microfibers

Photochromic spiropyran molecules were embedded in electrospun polymer microfibers. Electrospinning of a clear viscous chloroform solution containing a spiropyran and a matrix polymer, such as polystyrene and polyethylene oxide, affords polymer microfibers that are photoswitchable. Photomasked, 365 nm UV irradiation of the microfibers results in the generation of patterned color images owing to the selective transformation of the spiropyran molecules from their ring‐closed SP to ring‐opened MC form. The UV‐irradiated areas display brilliant red fluorescence, which changes to green fluorescence upon prolonged irradiation.

     

Synthesis of New Spiropyrans With a Polyaromatic or Heteroaromatic Pendant and Their Photochromic Bedhaviors

A series of spiropyrans with a polyaromatic or heteroaromatic pendant was synthesized conveniently.Their photochromic behaviors were investigated with the aid of absorption spectral measurements.The results indicated that the compounds with the same parent spiropyran but different aromatic pendant show significantly different photochromic properties.This may be due to the π-π orbital interaction between the polyaromatic pendant and the open photomerocyanine form of spiropyran.The results obtained are very useful in the molecule design area.     

In situ Observation of the Photochromism in the Langmuir Monolayer of a Non—typical Amphiphilic Spiropyran Derivative at the Air／Water Interface

In situ photochromic process in the monolayer of aphotochromic spiropyran derivative without long alkyl chain,was investigated.The photochromism at the air/water interface under differnet surface pressures was studied by surface pressure-area isotherms,surface pressure-time curves,area-time curves and Brewster angle microscopy.Both forms of the compound were found to form monolayers at the air/water interface althouhg it does not have long alkyl chain.A large area expansion in the monolayer corresponding to a zreo^th order reaction was found at the initial stage of the UV light irradiation.A series of dynamic investigations revealed that at high pressure after phase transition in the monolayer,the surface pressure changes greatly umder alternative irradiation of UV and visible light.An obvious morphological change accompanying with the photochromism was observed in situ.     

Spiropyran Photoswitches in the Context of DNA: Synthesis and Photochromic Properties

A new design is presented for the incorporation of spiropyran photoswitches into nucleic acids by oligonucleotide solid phase synthesis. This design enables interaction of the 6‐nitrospirobenzopyran (NitroBIPS) photoswitch with the adjacent nucleobases and leaves the photochemical properties of NitroBIPS intact. UV/Vis spectroscopy and HPLC revealed that NitroBIPS incorporated into DNA consists of up to 40 % merocyanine in its thermal equilibrium and undergoes reversible switching between the photoisomeric spiropyran (SP) and merocyanin (MC) state by alternating excitation using visible light or heat for at least fifteen switching cycles. Exchanging the chromene part of NitroBIPS on the DNA level gives access to differently substituted spiropyran derivatives allowing the screening for spiropyrans with suitable properties in a straightforward manner. Thus, by incorporating the highly hydrolysis‐stable pyrido‐spiropyran derivative PyBIPS pure light‐triggered reversible switching of a spiropyran in DNA has been realized for the first time. Therefore, this design represents a new useful platform for investigating the photochromic behavior of different spiropyran photoswitches in a nucleic acid environment and for using spiropyrans to induce light‐ or heat‐triggered changes in conformations or in fluorescence quenching properties of oligonucleotides.     

Excited State Proton Transfers in Hybrid Compound Based on Indoline Spiropyran of the Coumarin Type and Azomethinocoumarin in the Presence of Metal Ions

Spectral-luminescence properties of a hybrid compound containing a coumarin-type spiropyran and an azomethinocoumarin fragment in toluene-acetonitrile solution in the presence of Li⁺, Ca²⁺, Zn²⁺ and Mg²⁺ ions are reported. Two excited state proton transfers can occur in the hybrid compound—the transfer of a proton from the OH group of the 7-hydroxy coumarin tautomer to the N atom of the C=N bond of the azomethine fragment leading to green ESIPT fluorescence with a maximum at 540 nm and from the OH group of the 7-hydroxy coumarin tautomer to the carbonyl group of the pyrone chromophore, which leads to the formation of the 2-hydroxyl-tautomer T of coumarin with blue fluorescence with a maximum at 475 nm. Dependence of these excited state proton transfers on the metal nature and irradiation with an external UV source is discussed.