稀土Eu(Ⅲ)双酞菁衍生物LB膜的荧光性

合成了八－４－（四氢糠氧基）酞菁铕（Ⅲ）,通过元素分析、红外光谱、质谱和紫外－可见光谱加以确认。测定了配合物的ＩＩ－Ａ曲线,证明它有很好的成膜性,Ｚ型沉积形成的ＬＢ膜材料有很强的荧光响应,随着ＬＢ膜厚度的增加,荧光性增强。掺杂邻菲咯啉形成的混合ＬＢ膜,其荧光性比纯膜强。但不是邻菲咯啉加入的量越多荧光性越强。配合物：邻菲咯啉＝１：１０时（摩尔比）,有最好的荧光行为。用电子光谱对ＬＢ膜的结构进行了表征     

Effect of peripheral hydrophobic alkoxy substitution on the organic field effect transistor performance of amphiphilic tris(phthalocyaninato) europium triple-decker complexes

A series of four amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with different lengths of hydrophobic alkoxy substituents on one outer phthalocyanine ligand [Pc(15C5)4]Eu[Pc(15C5)4]Eu[Pc(OCnH(2n+1))8] (n = 4, 6, 10,12) (1, 2, 4, and 5) was designed and prepared. Their film forming and organic field effect transistor properties have been systematically studied in comparison with analogous [Pc(15C5)4]Eu[Pc(15C5)4]Eu[Pc(OC8H17)8] (3). Experimental results showed that all these typical amphiphilic sandwich triple-decker molecules have been fabricated into highly ordered films by the Langmuir-Blodgett (LB) technique, which displays carrier mobility in the direction parallel to the aromatic phthalocyanine rings in the range of 0.0032-0.60 cm2 V(-1) s(-1) depending on the length of the hydrophobic alkoxy substituents. This is rationalized on the basis of comparative morphology analysis results of the LB films by the atomic force microscopy technique.     

四（2,4—二叔戊基苯氧基）酞菁铜（Ⅱ）的合成及其LB膜

合成了标题酞菁铜衍生物,并通过元素分析,高压液相色谱,紫外光谱,红外光谱,核磁共振谱,电镜,顺磁共振谱及质谱加以确认。该化合物在稀氯仿溶液和LB膜中各以单,双分子缔合的形式存在。Z型沉积形成的单层LB膜对氨气有很高的灵敏度和选择性。     

新型两亲性酞菁锌LB膜的研究

本文合成了一种新型的两亲性酞菁分子,研究了它在不同溶剂中的聚集行为,考察了酞菁及酞菁与正十六烷混合的成膜性能,制备了混合的多层LB膜,并利用紫外光谱研究LB膜内的分子聚集状况,用分子激子理论对实验结果加以分析,还应用偏振紫外的方法对LB膜内酞菁分子大环的取向进行了确定。     

Exploiting distinct molecular architectures of ultrathin films made with iron phthalocyanine for sensing

The possibility of generating distinct film properties from the same material is crucial for a number of applications, which can only be achieved by controlling the molecular architecture. In this paper we demonstrate as a proof-of-principle that ultrathin films produced from iron phthalocyanine (FePc) may be used to detect trace amounts of copper ions in water, where advantage was taken of the cross sensitivity of the sensing units that displayed distinct electrical properties. The ultrathin films were fabricated with three methods, namely physical vapor deposition (PVD), Langmuir-Blodgett (LB), and electrostatic layer-by-layer (LbL) techniques, where for the latter tetrasulfonated phthalocyanine was used (FeTsPc). PVD and LB films were more homogeneous than the LbL films at both microscopic and nanoscopic scales, according to results from micro-Raman spectroscopy and atomic force microscopy (AFM), respectively. From FTIR spectroscopy data, these more homogeneous films were found to have FePc molecules oriented preferentially, tilted in relation to the substrate surface, while FeTsPc molecules were isotropically distributed in the LbL films. Impedance spectroscopy measurements with films adsorbed onto interdigitated gold electrodes indicated that the electrical response depends on the type of film-forming method and varies with incorporation of copper ions in aqueous solutions. Using principal component analysis (PCA), we were able to exploit the cross sensitivity of the sensing units and detect copper ions (Cu(2+)) down to 0.2 mg/L, not only in ultrapure water but also in distilled and tap water. This level of sensitivity is sufficient for quality control of water for human consumption, with a fast, low-cost method.     

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging.     

酞菁铜化合物LB膜的制备及结构形态研究

利用LB技术研究了带有4个长碳氢链的酞菁铜化合物(CuC12Pc)的单分子膜及它与十八胺(ODA)、二十酸(AA)的混合LB膜的聚集结构形态. 结果表明这种酞菁铜化合物在气液界面上可以形成比较稳定有序的双层Langmuir膜, 且可以转移质量较好的多层LB膜. 利用原子力显微镜(AFM)研究了酞菁铜分子的聚集体结构, 发现CuC12Pc/AA混合膜表现为网状的聚集结构, 而CuC12Pc/ODA混合膜形成长岛颗粒状聚集, 并结合UV-Vis吸收光谱讨论了酞菁铜分子形成不同聚集结构的原因.     

The cis-bis(decanoate)tin phthalocyanine/DPPC film at the air/water interface

Films made of cis-bis-decanoate-tin(IV) phthalocyanine (PcSn10) and racemic dipalmitoylphosphatidylcholine (DPPC) are studied with compression isotherms and Brewster angle microscopy (BAM) at the air/water interface. Films enriched in PcSn10 present phase separation elliptical-shaped domains. These domains present optical anisotropy and molecular order. They are enriched in PcSn10, and the film outside these domains is enriched in DPPC, as shown in by high-angle annular dark-field transmission electron microscopy on Langmuir-Blodgett (LB) transferred films. Film collapse area and atomic force microscopy images of LB transferred films on mica indicate that the films are actually multilayers. A computational survey was performed to determine how the PcSn10 molecules prefer to self-assemble, in films basically made of PcSn10. The relative energetic stability for several dimeric assemblies was obtained, and a crystal model of the film was developed through packing and repeating the PcSn10 molecules, along the crystallographic directions of the unit cell. Our results contribute to understanding the strong interaction between PcSn10 and DPPC at the air/water interface, where even small quantities of DPPC (~1-2%) can modify the film in an important way.     

Multifunctional Langmuir-Blodgett film of an Amphiphilic Benziminazole Styryl Dye

IntroductionA considerable interest has been focused ondesigning organic crystals with multiproperty suchas conductivity,magnetism,and nonlinear opticalresponse[1,2 ] ,but there have been less reports ondesigning multifunctional Langmuir- Blodgett( LB)films[3 ] .In recent years,our group has found thatLB films of some dyes with a donor-π electronbridge- acceptor ( D-π- A ) structure such ashemicyanine dyes exhibit good photoelectricconversion properties besides their well- knownhigh secon…     

Polyoxometalate monolayers in Langmuir-Blodgett films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.     

In situ visible spectroscopy of a gadolinium bisphthalocyanine LB film exposed to chlorine gas

We report the preparation of Langmuir-Blodgett (LB) films of a gadolinium phthalocyanine, doubledecker, molecular sandwich-type complex [Gd(Pc)₂] and its ultraviolet-visible spectroscopic characterisation. We have studied the changes in the optical absorbance spectra that occur upon exposure to very low concentrations (~10 ppm) of chlorine gas. The main absorption band in the visible region occurs at ~690 nm. Upon exposure to chlorine gas, the intensity of this band decreases with the simultaneous introduction of a new peak at ~734 nm, an isosbestic point occurring at 721 nm. These spectral changes are indicative of oxidation of the complex by chlorine to form the [Gd(Pc)₂]⁺ species. The kinetics of this response suggest that the adsorption of chlorine by the LB film is a complex process, possibly involving up to three independent mechanisms. The LB film recovers almost fully (> 95%) upon switching off the chlorine supply.     

Molecules of synthesized phthalocyanine as a material for the detection of 2,4-toluene diisocyanate (TDI)

Various numbers of LB monolayers of a metal-free phthalocyanine derivative, A410H₂Pc, have been deposited onto ultrasonically cleaned quartz substrates with platinum interdigitated electrodes. Similar devices i.e. those with the same number of LB layers, show the same response characteristics in the presence of 35 ppb (0.035 ppm) toluene diisocyanate (TDI)—a toxic substance used in the production of plastics and found in certain types of paint. The response times of the LB devices studied so far have been calculated to be about 40s. The electrical properties of evaporated films of a metal-free phthalocyanine derivative, α-H₂Pc, and those of the A410H₂Pc LB films have been found to be similar. The response time for the evaporated films has been found to be much less that that for the LB films. Although a direct comparison cannot be made between the LB and evaporated films, in this case, results suggest that devices fabricated from evaporated films will be much faster at detecting the presence of TDI than devices fabricated from LB films.     

Tetrakis-4-(2,4-di-tertamylphenoxy)phthalo-cyaninato-polysiloxane Langmuir-Blodgett Films and Their Gas Sensitive Properties

Tetrakis-4-(2,4-di-amylphenoxy) phthalocyaninato-polysiloxane (R₁PcPS) Langmuir-Blodgett (LB) films were prepared onto planar interdigital microelectrode arrays and their pas sensitive, properties were investigated. The results of response and recovery process were Shown when the (R₁PcPS) LB films were exposed to NH₃, NO₂ and I₂ gas in air. THh gas sensitive sensor consisting of (R₁PcPS) LB film can be used to detect NH₃ gas down to 0.0005% in air.     

Electrochemical properties of a ruthenium complex immobilized as thin films and in carbon paste electrodes

The electrochemical properties of mer-[RuCl₃(dppb)(4-pic)] (dppb = Ph₂P(CH₂)₄PPh₂, 4-pic = CH₃C₅H₄N), Rupic, in CHCl₃ are governed by the formation of species such as [Ru₂Cl₅(dppb)₂], [Ru₂(dppb)₂Cl₄(4-pic)] and trans-[RuCl₂(dppb)(4-pic)₂] upon the reduction of “[RuCl₂(dppb)]”. The overall behavior depends on whether Rupic is immobilized in cast or Langmuir–Blodgett (LB) films, or incorporated into a carbon paste electrode (CPE). In cyclic voltammograms, one redox process appears for LB/Rupic films and CPE/Rupic, at E_pa = 0.35 V, E_pc = 0.25 V vs SCE, and E_pa = 0.32 V, E_pc = 0.24 V vs Ag/AgCl, respectively. This redox process was ascribed to the Ru^III/Ru^II charge transfer. For cast films the redox pair was poorly defined, with E_pa = 0.27 V and E_pc = 0.20 V. The reason for the difference lies in the phase separation and formation of aggregates onto ITO for the cast film, in contrast to the LB film. With aggregation, the formation of species occurring in solution is impaired for Rupic in cast films. The electrochemical properties for Rupic in LB films and incorporated into CPE allowed the electrocatalytic activity of Rupic to be exploited in sensors for dopamine and ascorbic acid.     

Columnar self-assembly and alignment of planar carbenium ions in Langmuir-Blodgett films

Structural and optical properties of multilayer Langmuir-Blodgett (LB) films of two amphiphilic carbenium salts 2-didecylamino-6,10-bis(dimethylamino)-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-1) and 2,6-bis(decylmethylamino)-10-dimethylamino-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-2) are described. The LB films were prepared on lipophilic glass by standard vertical dipping. Grazing incidence X-ray diffraction (GIXD) measurements show that the planar organic cores, in spite of their positive charge, form closely packed columns with a repeating distance of ～3.45 ?. Specular X-ray reflectivity (SXR) reveals the LB multilayers to consist of Y-type bilayers with thickness 31 ? for ATOTA-1 and 41 ? for ATOTA-2. This significant difference is ascribed to the different packing motifs of the alkyl chains in the two LB films. GIXD and polarized UV-vis absorption and emission spectroscopy show that the columnar aggregates in the LB films are oriented along the dipping direction. This alignment is attributed to shear effects during LB transfer. The main absorption band of the LB films is blue-shifted compared to that in solution, while the fluorescence is red-shifted by more than 100 nm. These findings suggest the presence of H-aggregates in agreement with the cofacial packing derived from the X-ray measurements. Polarized absorption spectroscopy with variable angle of incidence was used to resolve two perpendicular optical transitions in the visible range, one at 460 nm polarized perpendicular to the columnar direction, in the plane of the film, and one at 420 nm polarized along the film normal.     

液晶聚合物的单层与Langmuir-Blodgett膜

系统研究了手性液晶聚硅氧烷和光致变色液晶聚硅氧烷两个毓的侧链液晶聚合物在空气/水界面的单层行为和Langmuir-Blodgett(LB)膜沉积特性,对LB膜结构与存在的聚集现象进行了系统的表征,并初步探讨了LB膜中液晶聚合物表现的功能性。     

Studies of Langmuir-Blodgett films of an ion pair metal complex containing Eu(III)-Ru(II) dual chromophores

A surfactant ion-pair complex, [Ru(bpy)(2)L][Eu(NTA)(4)](2) (in which L = 1-docosyl-2-(2- pyridyl)benzimidazole, bpy = 2,2'-bipyridine, and NTA = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionato) has been synthesized. The surface pressure-area isotherm measurements show that the complex forms a stable Langmuir film at the air-water interface without adding any electrolytes into the subphase. The monolayers formed at the surface pressures of 5 mN m(-1) and 20 mN m(-1), have been successfully transferred onto glass and quartz substrates with the transfer ratios close to unity. The Langmuir-Blodgett films were studied by UV-visible, infrared, and emission spectroscopies, atomic force microscopy, and cyclic voltammetry. The optical, redox, and morphology properties of the LB films were found to be significantly affected by the target surface pressures used for the film depositions.     

Enhanced optical and nonlinear optical responses in a polyelectrolyte templated Langmuir-Blodgett film

Optical and nonlinear optical properties like fluorescence and second harmonic generation (SHG) of molecular materials can be strongly influenced by the mode of assembly of the molecules. The Langmuir-Blodgett (LB) technique is an elegant route to the controlled assembly of molecules in ultrathin films, and complexation of ionic amphiphiles in the Langmuir film by polyions introduced in the aqueous subphase provides a simple and efficient access to further control, stabilization, and optimization. The monolayer LB film of the hemicyanine-based amphiphile, N-n-octadecyl-4-[2-(4-(N,N-ethyloctadecylamino)phenyl)ethenyl]pyridinium possessing a "tail-head-tail" structure, shows fluorescence as well as SHG response. The concomitant enhancement of both of these linear and nonlinear optical attributes is achieved through templating with the polyanion of carboxymethylcellulose. Brewster angle and atomic force microscopy reveal the influence of polyelectrolyte templating on the morphology of the Langmuir and LB films. Polarized absorption and fluorescence spectroscopy provide insight into the impact of complexation with the polyelectrolyte on the orientation and deaggregation of the hemicyanine headgroup leading to fluorescence and SHG enhancement in the LB film.     

Photoelectrical properties of Langmuir–Blodgett films of poly(methyl phenylsilane)s

Langmuir–Blodgett (LB) films were prepared from poly(methylphenylsilane) bearing electron acceptor π-conjugated substituents. The small limiting area (0.078 nm²) per one repeating unit of polysilane (PSi) in monomolecular film and the large thickness of the film (6 nm) suggest that the polymer chains are not fully spread on water surface. The electrical and photoelectrical properties of Al/LB film/Au sandwich cells containing various numbers of the polysilane layers were studied. Holes were transported from the Al electrode through the LB film to the Au electrode when the light was absorbed by the polysilane. The highest photovoltaic effect occurred in the first monolayer of polysilane at the Al contact. The cell resistivity and the photovoltage were decreased by parallel conductance of defects in the films consisting of small numbers of PSi layers.     

8-羟基喹啉镧两亲性配合物LB膜的双层电致发光器件

以具有不同层数的两亲配合物二[2-(N-十六烷基氨基甲酰基)-8-羟基喹啉]合镧[La(HQ)₂Cl]的LB膜为发光层,PBD为电子传输层,制备了双层结构的电致发光(EL)器件:ITO/LB膜/PBD/Al.器件产生黄绿色注入式发光.LB膜的层数和沉积压对器件的性能具有重要影响.在16V激发电压下,5,11和21层LB膜双层EL器件的电流密度分别为48,29和16.4mA/cm²,启亮电压阀值为7.5,8.5和9.5V.器件的亮度随电流密度和驱动电压的增加而增加.在相同偏压下,21层LB膜EL器件的亮度大于5和11层LB膜的器件.在25mN/m沉积的LB膜制备的EL器件具有较高的亮度(1219cd/m₂)和击穿电压.