Self-aggregates formation of tetrachloroperylene acid esters in Langmuir and Langmuir-Blodgett films

Using Langmuir and Langmuir-Blodgett techniques molecular films of chlorinated perylene derivatives, namely tetra-n-butyl-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylate (PCn for n = 1, 5, 9) have been studied. The Langmuir films of pure compounds and mixed with liquid crystalline 4-octyl-4′-cyanobiphenyl (8CB) were characterized by surface pressure-mean molecular area isotherms. An additive rule reveals miscibility of all the dyes with 8CB but shows different types of intermolecular interaction forces. The pure and mixed Langmuir films were transferred onto quartz plates and characterized spectroscopically. Absorption and fluorescence spectra were recorded for the samples in form of diluted chloroform solution, the dye with 8CB mixtures in monomolecular Langmuir-Blodgett films and in liquid crystal cells. Different tendency to aggregation of the dye with short and long alkyl chains was observed. It is shown that the dye molecule stacking and aggregation of the chlorinated perylene dyes depend on the dye concentration and are related to the torsion of the perylene core.     

Spectral properties of naphthalimide dyes mixed with 4-heptyl-4′-cyanobiphenyl (7CB) in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some fluorescent dyes, namely derivatives of 4-aminonaphthalimide, and their binary mixtures with the liquid crystal 4-heptyl-4′-cyanobiphenyl (7CB) have been studied. The electronic absorption and fluorescence spectra were recorded. On the basis of these spectra, the spectral properties of the dyes and the intermolecular interactions in ultrathin ordered films were determined. The conclusions about the tendency to the creation of aggregates by dye molecules in LB films have been drawn. The measurements of absorption by using linearly polarised light have allowed us to determine the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface.     

Self-aggregates formation of 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes and of their binary mixtures with the liquid crystal 4-octyl-4′-cyanobiphenyl (8CB) have been studied. Absorption and fluorescence studies were carried out. Both absorption and fluorescence spectra have revealed the formation of self-aggregates of dye molecules in monomolecular layers. Moreover, information about the molecular organization at the air-solid substrate interface has been obtained.     

红外光谱研究聚硅氧烷侧链手性液晶及其单体的单层LB膜

一种聚硅氧烷侧链手性液晶P及其单体M的单层LB膜分别在11mN/m和8mN/m的表面压力下,从水汽界面成功地转移到在镀金玻璃片和氟化钙基片上。π-A曲线表明P及其单体M在水汽界面上单层膜的崩溃压力分别是35和11mN/m。红外透过和反射吸收光谱表明两者的生色团部分及烷基链部分倾斜排列在固体基片上,但其倾斜角不同。M比P有更大的倾斜角。同时,不论P或M其烷基链的轴向与芳香核部分的长轴方向并不重合。P的烷基链比M的烷基链更有序。     

Intermolecular interactions in Langmuir-Blodget films of liquid crystalline perylene derivatives

Langmuir-Blodgett (LB) films formed of some discotic liquid crystals, namely 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes, mixed with arachid acid have been studied. The absorption and fluorescence spectra were recorded. The results obtained have led to conclusions about formation of self-aggregates of dye molecules both in ground and excited states at the air-solid substrate interface. It was found that some fraction of J-aggregates can be created in the ground state. In the excited state, mostly excimers appear and the number of this kind of aggregates depends on the length of the alkyl chains substituted to the perylene core, as well as on the dye concentration and the number of layers in LB films.     

Thermodynamic properties of Langmuir layers created of monoimide perylenetetracarboxylic acid derivatives

Langmuir films formed of some fluorescent dyes, 3,4-bis-pentyl ester of 9,10-N-(n-pentylimide)-perylenetetracarboxylic acid, as well as their mixtures with arachidic acid, were studied. Surface pressure versus mean molecular area isotherms for Langmuir films were reordered and the alignment of molecules at the air–water interface was estimated. The isotherms show that the dye molecules do not lie flat onto the water surface but are tilted with respect to the normal to the interface. The surface pressure–area isotherms of Langmuir films formed from the dye/arachidic acid mixture provide evidence for phase separation of the components within almost the entire range of mole fractions. A repulsive interaction between molecules was observed in all two components of Langmuir films.     

偶氮染料掺杂高分子薄膜的光谱和光存储性质研究

利用旋涂法,制备了以二乙基胺基〖Ｎ（ＣＨ２ＣＨ３）２〗作为推电子基因、以具有强电负性的羧基（ＣＯＯＨ）作为拉电子基团的推－拉型偶氮染料掺杂的高分子（ＰＭＭＡ）薄膜。在室温下测试了该偶氮染料在溶液和薄膜态的吸收光谱、薄膜态的反射光谱和透过光,发现该薄膜在４００～５５０ｎｍ波长范围内具有强的吸收。在５１４．５ｎｍ光盘静脉测试仪上测试了膜片的静脉光存储性能,结果表明,用低功率Ａｒ＾＋激光（５１４．５ｎ     

4-硝基-4′-氨基偶氮苯的光学性质研究

采用紫外可见吸收和二次谐波产生技术研究了“推-拉”型偶氮苯分子Langmuir-Blodgett(LB)膜的光谱和二阶非线性光学特性.4-硝基-4′-氨基偶氮苯(NAA)分子能制成很好的LB多层膜,在稀溶液中以单体的反式异构体形式存在,在膜中主要以J-聚集体的形式存在,LB膜的紫外可见吸收谱的吸收峰较之溶液的发生了52 nm的红移.NAALB膜的二阶非线性极化率χ(2)为19.59×10－8 esu,一阶超极化率β值较大,约为1.974×10－29 esu.其光学二阶非线性起源于电偶极子机制.     

半花菁衍生物LB膜的非线性光学性能研究

本文利用二次谐波产生、紫外－可见吸收光谱、Ⅱ－Ａ曲线等方法，探讨了四种分子结构相近的半花菁染料衍生物ＬＢ膜的非线性光学性能。研究了它们的分子结构与β值大小的关系，分析了引起β值变化的主要原因，证实了极性基团的强弱顺序。并讨论了ＬＢ膜中聚集效应程度不同的原因。通过光学二次谐波信号强度与膜层数的关系，对比了样品的成膜性能。     

Oriental behaviour of some homologues of 4-n-pentyl-phenylthio-4′-n-alkoxybenzoate doped with dichroic dye

The long-range orientational order of three members of 4-n-pentylphenylthio-4′-n-alkoxybenzoate series doped with a dichroic dye was studied by means of electronic absorption and fluorescence measurements. The order parameters <P₂> and <P₄> as well as the orientational distribution function were determined on the basis of absorption and emission spectra of linearly polarized light recorded as a function of temperature in the nematic, smectic A, and smectic C phases. An influence of the dye molecular structure on the orientational order of the dye/liquid crystal mixture was observed. Moreover, the dependence of the order parameter values on the length of the alkoxy chain in liquid crystal molecules was found. It was shown that the order parameter <P₄>, obtained from fluorescence measurements, can be helpful in recognizing the second-order or weakly first-order transitions between various liquid crystalline phases.     

J-aggregates of thiacyanine dye organized in LB films: Effect of irradiation of light

In the present communication we report the preparation and characterizations of Langmuir and Langmuir-Blodgett films of a thiacyanine dye N,N′-dioctadecyl thiacyanine perchlorate (NK) mixed with Octadecyl trimethyl ammonium bromide (OTAB). The relationship between the molar ratio of OTAB and NK and the orientation of molecules at the air-water interface was investigated using surface pressure-area per molecule (π-A) isotherm. UV-vis absorption and fluorescence spectroscopic investigations reveal that prominent J-aggregation of NK molecule was observed in the LB films lifted at higher surface pressure. This J-aggregation can be controlled by diluting the NK molecules with OTAB. It was observed that the J-aggregates of NK decayed to monomer and H-aggregates when the NK-LB film was exposed to a monochromatic light of wavelength 460 nm (λ_max of J-aggregates).     

基于超分子结构共掺杂纳米复合薄膜的制备与荧光特性

为改善功能分了的特性,提出一种基于金属纳米粒子-偶氮染料复合物共掺杂超分子结构功能材料的设计新方法.并依照此方法制备出复合材料,观测了其显微结构,测量了其紫外-可见光吸收,研究了该超分子结构复合体系的荧光特性.实验发现,由于金属银纳米粒子的掺杂,使得超分子结构复合体系中功能分子甲基橙在溶液态体系的荧光强度增强近5倍,而在两种不同结构(共混结构和包覆结构)的薄膜态超分子结构体系中,其荧光强度分别被猝灭15%和20%.研究结果表明,复合膜中采用超分子结构完全能够改善功能分子的特性.     

聚酰亚胺LB膜上液晶表面锚定的研究

通过测试光延迟研究了聚酰亚胺ＬＢ膜的光学各向异性，分析了在ＬＢ膜成膜过程中成膜分子的流动取向特性，并研究了液晶的表面锚定能，分析了ＬＢ膜上液晶的取向机制．聚酰亚胺ＬＢ膜的链段的取向程度较强摩擦情形的聚酰亚胺表面的链段取向要差．强摩擦的聚酰亚胺会比聚酰亚胺ＬＢ膜具有更好的排列液晶分子的能力．ＬＢ膜的流动取向模式使得聚酰亚胺成膜分子沿拉伸方向形成一定的有序排列，并诱导液晶分子定向排列，液晶和聚合物分子相互作用是液晶表面排列的主要动力 关键词：     

Impacts of pH and molecular structure on ultrasonic degradation of azo dyes

Sonochemical bleaching of monoazo dyes was investigated by irradiating 30 microM solutions of two "aryl-azo-naphthol" type model dyes in acidic, neutral and basic conditions using a 300 kHz emitter. It was found that the rate of bleaching in all cases was first order with respect to the maximum absorption of the dye in the visible band, and accelerated with increased acidity. The inhibition observed at alkaline conditions was attributed to the formation of anionic dye structures and their competition with the dye and its intermediate oxidation products for hydroxyl radicals, which are the major precursors of azo dye oxidation in sonicated water. Decolorization of the dyes was also related to the size of the molecule and the type or position of substituents about azo bonds. Comparison of color decay rates at similar conditions showed that the dye with a simple structure, low molecular mass and one ortho-substituent (hydroxyl) about the azo bond bleached considerably faster than the one having a more complicated structure (higher mass) and an additional o-substituent to the azo bond other than the OH group.     

光谱法研究入—4—（十六烷氧基）双酞菁镧的LB膜

测定了八－４－（十六烷氧基）双酞菁镧氯仿溶液在亚相水面上的π￣Ａ曲线，同时制备了它的ＬＢ膜。应用红外光谱及紫外－可见光谱法对其进行了研究。     

分子组装体的谱学研究

红外光谱、拉曼光谱、荧光光谱、紫外可见吸收光谱等是研究结构的主要手段。由于振动光谱得到的是力常数的信息 ,因而可以直接获得分子内、分子间键的信息 ,电子光谱则可以获取体系电子结构的信息 ,因而是分子组装体研究的重要方法手段。然而分子光谱也有其自身的限制 ,由于需要了解单层膜、单层膜与基底、单层膜与多层膜之间相互作用的信息 ,这些体系由于样品量小、信号弱 ,因此需要建立相应的适用于分子组装体的高灵敏度的特殊检测方法和实验技术 ,并发展分析分子间弱相互作用的光谱分析理论。本文综述了吉林大学超分子结构与谱学开放实验室近几年在超薄膜谱学方面的研究工作和进展。     

Langmuir-Blodgett film structure

Langmuir-Blodgett (LB) films occupy a unique niche at the crossroads of materials science, complex fluids, and biophysics. They have many similarities to inorganic epitaxial films due to the layer by layer deposition process; however, the amphiphilic nature of the constituent molecules provides the connection to lyotropic liquid crystals and membranes. A great deal is known about LB film structure and thermodynamic behavior; both from classical studies as well as from recent experiments using sophisticated characterization techniques such as synchrotron X-ray scattering and scanning probe microscopy. This article summarizes the current understanding of these systems from a physical/structural point of view. Included are discussions of the deposition process, the layered nature of LB films, intralayer molecular packing, defects, stability, and phase transitions.     

Modeling the structure and spectral properties of sensitizing black dye for nanocrystalline TiO<Subscript>2</Subscript> solar cells

Spectral and electronic properties of a sensitizing black dye; a 4,4′,4′′-tricarboxy-2,2′:6′,2′-terpyridine)tris(isocyanato) ruthenium(II) complex; for nanocrystalline TiO₂ solar cells have been investigated by modern methods of quantum chemistry. The light absorption mechanism in the lowest excited triplet states of the dye was studied. The efficiency of electron injection into nanocrystalline TiO₂ is shown to depend on both the nature of charge-transfer states and asymmetric deformation of an excited triplet term of the black dye.     

4-戊基-4'-氰基联苯液晶的分子二阶非线性光学极化率测量方法

在玻璃衬底上制得单层硬脂酸的Langmuir-Blodgett(LB)膜,做为4-戊基-4''-氰基联苯(5CB)液晶的取向层,在取向层上旋涂一层5CB液晶,用透射二次谐波方法测量出5CB液晶分子二阶非线性光学极化率,其值为β=7×10-29esu.对比文献值,测量得到的结果符合较好.     

Fabrication and Spectroscopic Characterization of Langmuir-Blodgett Films with Luminescent Rare Earth Complexes of Long Chain Double Functional Ligands Mono-L Phthalate (L = Hexadecyl, Octadecyl and Eicosyl)

In this paper, some novel long chain amphiphillic monoester molecules were designed to afford double functions: film-formation ability and luminescent sensitization ability. Subsequently organized molecular films of rare earth complexes with these functional ligands formulated as ML2NO3 were fabricated by the Langmuir-Blodgett film (LB) technology, where RE denotes rare earth ions Eu3+, Tb3+ and Dy3+; L denotes the long chain carboxylic ligands monohexadecyl phthalate (16-Phth), monooctadecyl phthalate (18-Phth) and monoeicosyl phthalate (20-Phth). The average molecular area was obtained according to the π-A isotherms. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction and the average layer spacing was determined from the Bragg equation. UV absorption intensity increases linearly with the number of LB films layers, which indicates that the LB films are homogeneously deposited. The fluorescence spectra of these LB films were quite different from those of their solid complexes. It reveals that the long chain ester ligands are suitable for the excited states of Tb3+ and Dy3+ in the LB films as well as in the solid complexes, but not match with the europium ion in the LB films.