桥环菁染料II:1-(N-烷基-4-吡啶基)-3-(N-烷基-4-吡啶亚基)-4,5-二取代-1,4-环戊二烯菁染料的合成和质子化及荧光性质研究

本文报道带有疏水长链的桥环菁染料的合成。并研究这类菁染料的质子化过程和平衡常数、取代效应, 以及胶束、糖淀粉和环糊精对染料的可见光谱及质子化过程的影响, 本文也考察了桥环菁染料的荧光光谱, 这些研究在理论上和实际应用有一定意义。     

桥环菁染料——Ⅱ.1-(N-烷基-4-吡啶鎓基)-3-(N-烷基-4-吡啶亚基)-4,5-二取代-1,4-环戊二烯菁染料的合成和质子化及荧光性质研究

本文报道带有疏水长链的桥环菁染料的合成.并研究这类菁染料的质子化过程和平衡常数、取代效应,以及胶束、糖淀粉和环糊精对染料的可见光谱及质子化过程的影响,本文也考察了桥环菁染料的荧光光谱,这些研究在理论上和实际应用有一定意义.     

若干1-(N-甲基-4-吡啶鎓基)-3-(N-甲基-4-吡啶亚基)-4-烷基环戊烯-1-酮-5菁化合物可见吸收光谱的溶剂效应

菁是一类很重要的离子型染料和感光材料,也有极少数可用作激光染料,绝大部价菁染料为直链分子。我们最近合成了一系列带有五员桥环的菁,并研究了这些桥环菁化合物的质子化平衡和荧光性质。     

含N-烷基吲哚环方酸菁染料的合成及性能

本文合成了七个N-烷基取代吲哚环的方酸菁染料,通过红外光谱、核磁共振氢谱、质谱与元素分析确认其结构。测定它们的电子吸收光谱、熔点、溶解度和光褪色。结果表明共轭链上引入方酸桥环提高了光稳定性,N-烷基对染料的λmax的影响很小,但较大地改进了溶解度与熔点,带有支链的烷基有更好的溶解性能。     

若干1-(N-甲基-4-吡啶基)-3-(N-甲基-4-吡啶亚基)-4-烷基环戊烯-1-1酮)-5-菁化合物可见吸收光谱的溶剂效应

本文用岛津UV-26 型紫外可见分光光度仪研究了桥环菁化合物吸收光谱的溶剂效应, 并探讨了该类菁作为一种新的溶剂极性标度探针的可能性。     

冠醚菁染料的研究 Ⅵ.含苯并咪唑环的冠醚菁染料的合成

关于冠醚硫碳菁染料的合成及其光谱增感作用的研究已有报道.这类含冠醚结构因子的新型菁染料被证明具有良好的增感性能和稳定性. 为了进一步研究冠醚结构对菁染料感光性能和理化性能的影响,合成了含苯并咪唑环的冠醚咪碳菁染料以及与菁有关的冠醚苯乙烯型染料. 新染料1—7的结构得到质谱、核磁共振谱、红外和紫外光谱的证实.染料中间体季铵盐8的合成已在前文报道.     

方酸菁染料的合成

方酸菁染料业经证明具有光谱增感作用,但迄今未见其作为照相材料应用的报道.1973年法国Siegfried等将其用于巨脉冲红宝石激光的无源切换;最近Morel等又研究了它们在太阳能电池中的应用.作者合成了八个方酸菁染料,并对它们的照相性能和光电转换特性作了初步研究;发现其中的个别化合物不但具有良好的光谱增感作用,而且与照相工业中常用的染料“1833”相比,衰退也比较慢;部分化合物还表现出相当高的光电转换效率. 作者曾报道方酸的合成.本文介绍另一种方法,即以醋酸钠-醋酸环化1,1,3-三氯-2,     

三碳菁染料的研究

三碳菁染料的吸收在近红外区,可用作卤化银感光材料的红外增感染料,近年来在红外激光染料和光信息记录介质等方面也得到了开发及应用。在多甲川链上引入桥环可提高染料的稳定性。本文合成了9种含芳胺基取代的桥链三碳菁,讨论染料结构与其增感性能关系。     

苯乙烯基-4-吡啶菁染料的无溶剂微波合成

近年来随着人们对苯乙烯菁染料性质的深入了解,开始利用它的摩尔吸光系数高、光谱范围广以及荧光量子产率较高等特性,将其应用于激光染料、光盘存储材料和非线性光学材料[1～3]等.我们课题组从二十世纪七十年代中期开始一直从事苯乙烯染料、苯乙烯菁染料以及菁染料的合成及应用[4～7].     

氯取代硫三碳菁染料的合成及性能

本文合成了七个硫三碳菁.其中四个具有桥环的菁染料。测定了它们的电子吸收光谱,讨论了结构对光稳定性的影响。并发现镍络合物能有效地抑制菁染料的光退色。     

Synthesis and Visible Spectral Behaviour of Some New N‐Bridgehead Heterocyclic Cyanine Dyes Incorporating Pyrazolo (4,5‐b) Indolizine (Benzoindolizine)

The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and ¹³C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol.     

Bridged cyanine dyes. Part 1. 1-(N-methyl-4-pyridinio)-3-(N-methylpyridylene)cyclopenta-1,4-dienes

1,3-Bis(N-methyl-4-pyridinio)propane is condensed with a series of α-diketones to form deep red monocyanine dyes 8 . In strongly acidic solutions C-protonation occurs at the central carbon atom. A similar condensation with α-ketoesters yields zwitterionic cyanines 12 with extinction coefficients exceeding 10⁵.     

Bridged cyanine dyes. Part 2 . 1-(N-methyl-2-benzothiazolylinio)-3-(N-methyl-2-benzothiazolylene) and 1-(N-methyl-4-pyridinio)-3-(N-methyl-4-pyridylene)cyclopenta-1,4-dienes with fused rings

1,3-Bis(N-methyl-4-pyridyl)- and 1,3-bis(N-methyl-2-benzothiazolyl)-propane diiodides react with 1,2-cyclohexanedione, tetrachloro-1,2- and -1,4-benzoquinone, 2,3-dichloronaphthoquinone, 3,4-dichloromaleimide and 2,3-dichloroquinoxaline to give novel fused ring bridged cyanine dyes.     

Variations of fluorescence efficiencies of 9-(10H)-acridone and its 4-methoxy derivative with ph. excited-state proton transfer in very weak acids and

Acridone and its 4-methoxy derivative behave as very weak acids in their lowest excited singlet states. This behavior is shown to account for the pH dependences of their fluorescence spectra in alkaline solutions. 4-Methoxyacridone is also a very weak base in its lowest excited singlet state, which results in a pH dependence of its fluorescence spectrum in dilute acidic media. Acridone, although functioning as a very weak base in its lowest excited singlet state, in acidic ethanolic water, does not demonstrate excited-state proton exchange in acidic “pure” water. This suggests selective solvation by ethanol in the mixed solvent.     

Cyanine‐Like Dyes with Large Bond‐Length Alternation

Herein, the synthesis and properties of alkyne‐bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene‐bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR (¹H and ¹³C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond‐length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third‐order microscopic polarizability, of ?1.3×10^?33 esu for the alkyne‐linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two‐photon absorption spectra showed that the alkene‐bridged dye exhibited characteristics of cyanines, whereas the alkyne‐bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations.     

New cyanine-oligonucleotide conjugates: relationships between chemical structures and properties

Because the influence of the chemical structure of monomethine cyanine-oligo-2'-deoxyribonucleotide (ODN) conjugates on their binding and fluorescence properties has remained largely undetermined, we synthesized and studied a wide range of conjugates with various structural patterns. Different cyanine dyes such as thiocyanine, quinocyanine, and thiazole orange isomers were obtained. In the case of unsymmetrical cyanines, the linker was attached to either the quinoline or the benzothiazole nucleus. The influence of the ODN counterpart was evaluated by linking the cyanines to the 5'-end or to an internucleotidic phosphate. In the first case, the influence of neighboring nucleic bases was studied, whereas in the second, the stereochemical configuration at the phosphorus atom bearing the cyanine was investigated. We report here on relationships between the structures of the dyes and conjugates and some of their properties, such as the stability and fluorescence changes observed on their hybridization with the target sequence. This study provides useful information towards the design of ODN-cyanine conjugates.     

On the nature of excited electronic states in cyanine dyes: implications for visual pigment spectra

CNDO/S CI calculations are carried out on polyenes and on cyanine dyes. In contrast to polyenes, doubly excited configurations have a strong effect on the first optically allowed excited state in cyanines. Protonated Schiff bases of retinal are closely related to cyanine dyes, with important consequences for models of visual pigment spectra and photochemistry.     

咪碳菁类染料在溶液中的聚集行为

本文通过观察3种咪碳菁类染料在溶液中的聚集行为,从动力学角度分析了影响J 聚集形成的主要因素.     

Cyanine dyes from naphtho [1,2-6]thiazolo[3,2-d][1,4]thiazine

Deeply colored cyanine dyes have been synthesized from the previously unknown 3-methyl-12H-naphtho[1,2-b]thiazolo[3,2-d][1,4]thiazinium salts. It is assumed that the deep color of the new cyanines is connected with the conversion of the nonaromatic 1,4-thiazine ring in the dye molecule into an aromatic thiazine ring with three double bonds in a six-membered ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1282–1284, September, 1973.     

Regioselective oxidations of benzocarbaporphyrins with ferric chloride: a facile synthesis of bridged [18]annulene ketals with strong absorptions in the far red and an unexpected halogenation reaction at the interior carbon atom

Benzocarbaporphyrins 4 were found to undergo regioselective oxidations with ferric chloride in methanol, ethanol, isopropyl alcohol, or ethylene glycol to give bridged benzo[18]annulene ketal derivatives 5 in excellent yields. These polar derivatives were generally isolated in a monoprotonated form and the corresponding free bases appeared to be relatively unstable. Addition of TFA resulted in the formation of spectroscopically distinct dications. The ketals 5 were highly diatropic in nature, showing the internal alkoxy substituents upfield beyond -1 ppm in their proton NMR spectra. The external meso-protons resonated near 10 ppm, confirming the presence of a strong aromatic ring current. The UV-vis spectra for 5 showed a Soret band at 422 nm, and two strong absorptions in the far red at 751 and 832 nm. A carbaporphyrin with a fused acenaphthylene ring was also oxidized with ferric chloride and this produced a ketal derivative with still further bathochromically shifted absorptions particularly for the Soret band. Also, the use of different alcohols in these reactions allows the overall polarity of these ketal products to be controlled and this could have merit in biomedical applications. Reaction of carbaporphyrin 4a with aqueous ferric chloride afforded the corresponding 21-chloro derivative 20 in good yields, and at longer reaction times a nonaromatic dione was isolated. Aqueous ferric bromide gave a 21-bromocarbaporphyrin product but in this case very poor yields (<10%) were noted. Mechanisms are proposed to explain the formation of these unusual oxidation products. The structure of 21-chlorocarbaporphyrin 20 was further demonstrated by X-ray crystallography. The presence of the interior chlorine atom was found to tilt the indene moiety by 29.59(4) degrees relative to the [18]annulene macrocyclic ring. The crystal packing for 20 shows offset face-to-face pi-stacking interactions that link the porphyrinoid molecules as closely paired dimers.