Dis-aggregation of an insoluble porphyrin in a calixarene matrix: characterization of aggregate modes by extended dipole model

In this paper, the different aggregation modes of a water-insoluble porphyrin (EHO) mixed with an amphiphilic calix[8]arene (C8A), at the air-water interface and in Langmuir-Blodgett (LB) film form, are analyzed as a function of the mixed composition. The strategy used to control the EHO aggregation has consisted of preparing mixed thin films containing EHO and C8A, in different ratios, at the air-water interface. Therefore, the increase of the C8A molar ratio in the mixed film diminishes the aggregation of the EHO molecules, although such an effect must be exclusively related to the dilution of the porphyrin. The reflection spectra of the mixed C8A-EHO films registered at the air-water interface, show a complex Soret band exhibiting splitting, hypochromicity and broadening features. Also, during the transfer process at high surface pressure, it has been shown that the EHO molecules are ejected from the C8A monolayer and only a fraction of porphyrin is transferred to the solid support, in spite of a complete transfer for the C8A matrix. The complex structure of the reflection spectra at the air-water interface, as well as the polarization dependence of the absorption spectra for the mixed LB films, indicate the existence of four different arrangements for the EHO hosted in the C8A matrix. The aggregate formation is governed by two factors: the attraction between the porphyrin rings which minimizes their separation, and the alkyl chain interactions, that is, hydrophobic effect and/or steric hindrance which determine and restrict the possible aggregation structures. By using the extended dipole model, the assignment of the spectral peaks observed to different EHO aggregates is shown.     

Organization and properties of a conjugated poly(heteroarylene methines) at the air-water interface and in the Langmuir-Blodgett films

A poly(heteroarylene methine) derivative, poly[(2,5-thiophenediyl) (p-n-methyl, n-octylaminobenzylidene) (2,5-thiophenequinodimethaneiyl)] (PTABQ), has been synthesized and spread at the air-water interface. The influences of three kinds of solutions on PTABQ monolayer behavior at the air-water interface have been investigated via the measurements of the pi-A isotherm and film stability. The results show that all three kinds of PTABQ solutions are apt to form the stable and transferable monolayer film organized with the plane of its pi-system nearly perpendicular to the air-water interface. Moreover, the monolayer-forming ability of PTABQ can be improved by introducing a water-soluble amphiphilie as an extractable spread-aiding component, which is further proved by the AFM images and FTIR spectra of the transferred films. UV-visible absorption spectra indicate that the well-ordered layer-by-layer structure is successfully controlled in the LB films. The optical bandgap of PTABQ is reduced for the ordered arrangement of its molecules in LB films. The intrinsic electrical conductivity of PTABQ LB films is 8.1 x 10(-8) S/cm and the conductivity of iodine-doped films is 5.7 x 10(-7) S/cm.     

Molecular Arrangement of a Bolaamphiphilic Anthrancene Derivative in Langmuir-Blodgett Film

Langmuir monolayer at the air/water interface is the basis to understand the molecular arrangement and to fabricate the organized molecular films1. Bolaamphiphiles describes the molecules in which two head functional groups are linked by one or two hydrophobic chains2,3. In comparison with the one-headed amphiphile, abundant configurations of Langmuir monolayer are expected in bolaamphiphiles. Generally, three kinds of configurations of the Langmuir monolayers of bolaamphiphile at the air/w…     

J-aggregation and its characterization in Langmuir-Blodgett films of merocyanine dyes

Langmuir-Blodgett (LB) films are constructed by successively transferring monomolecular layers formed at the air-water interface onto solid substrates. One of the advantages of the LB technique in fabricating molecular aggregates lies in the fact that it can employ various kinds of molecules by mixing them at the air-water interface. The mixed system may exhibit new properties that are not observed for individual components. This method would be useful, for example, in the studies of the formation and control of the J-aggregates of functional dyes that attract attention both in science and technology. In this paper, I review this subject mainly based on our recent results in merocyanines. LB films of merocyanine dyes, mixed with arachidic acid (C(20)), exhibit J-aggregate formation and have been serving as typical systems in revealing the physical and structural aspects of nanosized molecular aggregates constructed as monolayers. In the case of LB films of a merocyanine dye having benzothiazole as donor nucleus (abbreviated as DS), electron spin resonance (ESR) spectroscopy has been successful in determining the characteristic in-plane orientation of dye molecules with respect to the dipping direction, which led to the discovery of the flow orientation effect during the dipping process of LB films as the origin of optical dichroism often observed in LB films. In this article, after an introduction of ESR spectroscopy, three major topics on the merocyanine J-aggregation and its characterization in mixed films are discussed. The first topic is the observation and control of the size of J-aggregates in the dilution limit of dyes in arachidic acid matrix for a methyl-substituted DS (6-Me-DS). Dependence of atomic force microscopy (AFM) patterns on the molar ratio allows the identification of dye domains. J-band optical peak analysis based on the Kuhn's extended dipole model, supplemented by a novel application of femtosecond pump-probe optical spectroscopy, yields the size of the J-aggregates of 10(3). The second topic is the control of the J-band peak wavelengths by mixing two different kinds of dye molecules. The first case is the mixture of a J-forming 6-Me-DS and non-J-forming merocyanine analog, DO with benzo-oxazole instead of benzothiazole of DS. The second case is the mixture of both J-forming dyes but with different J-band peak positions, 6-Me-DS and another analog of 5-Cl-DS. The optical peak shifts depending on the molar mixing ratio will be presented. The last topic is related to the elucidation of electronic states of dye molecules in the J-aggregates. Light-induced ESR (LESR) of DS films with stable isotope ((15)N or (13)C)-substituted dyes provide clear evidence for the photoinduced charge transfer by the detection of hyperfine structures. Moreover, infrared (IR) spectroscopy of (13)C-enriched dye identifies the IR absorption peak of the relevant carbon in the chromophore. The results give evidence for the enhanced intramolecular charge transfer of dyes in the J-aggregates compared with an isolated merocyanine composed of donor and acceptor moiety. Lastly, the Cl attachment in 5-Cl-DS leads to a significant enhancement of the nitrogen hyperfine coupling in the LESR spectra. These examples and others demonstrate the potential of LB films of merocyanines in the studies of the nanosized molecular aggregates in monolayer assemblies.     

Synthesis and supramolecular self-assembly study of a novel porphyrin molecule in Langmuir and Langmuir-Blodgett films

The self-assembly and supramolecular engineering of porphyrins into ordered arrays have recently attracted much interest because of their promising application potential in molecular and electronic devices, spintronics, energy harvesting and storage, catalysis, and sensor development. We herein report the synthesis and supramolecular self-assembly study of a novel porphyrin molecule, 2Por-TAZ, in Langmuir and Langmuir-Blodgett films. The 2Por-TAZ molecule contains two porphyrin macrocycles attached to a triaminotriazine headgroup. Triaminotriazines are known to form a highly ordered linear supramolecular self-assembly through complementary hydrogen bonding with barbituric acid molecules at the air-water interface. Surface pressure-area isotherm measurements and polarized UV-vis absorption spectroscopic studies indicate that the 2Por-TAZ molecules adopted an edge-on orientation at the air-water interface. Polarized UV-vis absorption study also revealed that the 2Por-TAZ molecules formed linear supramolecular networks on pure water and barbituric acid subphase with porphyrin flat planes facing toward the compression direction. The binding of barbituric acid with 2Por-TAZ molecules was observed from the expansion of the Langmuir monolayer film. Compared to the transferred LB film from pure water subphase, both the UV-vis absorbance and fluorescence emission intensity of the LB film transferred from barbituric acid subphase increased significantly.     

Formation, structure, and morphology of triazole-based Langmuir-Blodgett films

The formation, morphology, and structure of two-dimensional Langmuir-Blodgett (LB) assemblies of octadecyltriazole (ODT)-based metal-containing oligomers presenting, in the case of iron, the spin-crossover phenomenon is studied with Brewster angle microscopy, IR dichroism, X-ray diffraction, and atomic force microscopy. Two processes occurring at the air-water interface are confirmed to dominate the mechanism of formation of these LB films, the instability of the coordination polymers at the air-water interface and recoordination of metal ions in the subphase at the interface during the LB deposition process. The Langmuir film allowing the LB film formation is mostly made of ODT. The films do present a lamellar structure in which the ODT molecules are tilted and incorporate coordinated isolated metal ions and oligomers of metal ions. The morphology of the LB films is globally flat but with a rather high roughness resulting from inhomogeneities related to phenomena occurring during the LB film formation. These observations are in agreement with the relative affinity of the metal ions with ODT and the relative stability of the coordination polymers at the air-water interface, which have been determined for the group Cu-Fe-Co-Ni.     

J-aggregates in matrix stabilized two-dimensional azobenzene derivatives

A two-component film technique at the air-water interface has been used for fabricating matrix stabilized azobenzene J-aggregates. Langmuir monolayers of (E)-1-(3-chloro-4-(alkyloxy)phenyl)-2-phenyldiazene (CnCD, n=8,10,12) have been prepared with stearic acid (STA) as the two-dimensional matrix. Miscibility studies at a molecular level, explored from the monolayer pressure-area isotherms revealed a phase separation of the CnCD from the stearic acid matrix at a compression pressure of 10 mN/m. A 43-nm strong red shift in the 350 nm pi-pi * absorption feature implied formation of highly ordered J-aggregates of CnCDs in conformity with atomic force microscopy and micro-Raman spectral characteristics. While a one-component CnCD failed to form a 2D monolayer, the STA supported CnCD binary system crossed a mixed monolayer phase followed by compression, leading to the formation of matrix stabilized CnCD J-aggregates.     

Photoreactions and lateral patterning in Langmuir and Langmuir-Blodgett films

Reversible morphological changes occur with photoisomerization of azobenzene in Langmuir-Blodgett (LB) films complexed with polycations, which contradicts an implicit assumption of the concept of free volume that two-dimensional film structures are preserved during the photoisomerization. J-aggregates of chromophores are formed by two processes. The first process is "light-induced J-aggregation" in which photoisomerized molecules form J-aggregates. The other process is "triggered J-aggregation," in which photoisomerization of one of the components triggers J-aggregation of another chemical species in the mixed films. Both processes of J-aggregation are in many cases accompanied by large morphological changes of the films. However, LB films fabricated using processes under isobaric conditions do not change their morphology during light-induced J-aggregation and are patterned with J-aggregates using ultraviolet illumination through a photomask. Phase separation in mixed LB films gives rise to two-dimensional patterns, which are used to fabricate templates by using an amphiphilic silane-coupling agent as one of the components in the mixed LB films. Nanopatterns are also fabricated.     

Effect of water and air-water interface on the structural modification of Ni-arachidate Langmuir-Blodgett films

Nickel arachidate (NiA) Langmuir-Blodgett (LB) films have been deposited on hydrophilic Si(0 0 1) substrates by three (up-down-up) and five (up-down-up-down-up) strokes. During deposition, substrates were kept inside the water subphase for different times after each down stroke. Structural information of all the LB films have been obtained from X-ray reflectivity (XRR) studies. One and two symmetric monolayer (SML) was deposited on top of the asymmetric monolayer (AML) in three and five stokes respectively. All the preformed LB films were then used to go through the air-water interface with the same speed that was used at the time of film deposition. Structural information obtained from the XRR studies show that mainly the top layer density decreases after passing through the air-water interface but the layered structure remains the same. Information obtained from both the XRR and atomic force microscopy (AFM) studies suggest that molecules peeled from the top SML layer do not reincorporate with the LB film through tail-tail hydrophobic interaction. Our study shows that NiA LB film has better stability compared with cadmium arachidate LB film inside the water subphase without forming any out-of-plane molecular reorganization.     

三嵌段共聚物在气-液界面的有序组装

将氢化的苯乙烯(PS)/丁二烯(PB)/苯乙烯(PS)三嵌段共聚物(SEBS)磺化,得到磺化的SEBS(S－SEBS),在水亚相上铺展了S－SEBS的Langmuir膜,研究其π－A特性.制备S－SEBS的Langmuir－Blodgett(LB)膜,用原子力显微镜(AFM)对其表面形态进行了研究,并以芘作为荧光探针研究了溶液和膜中S－SEBS聚集态的变化.研究结果表明,S－SEBS在气－液界面可以形成由两亲性的纳米小球组装而成的有序的二维和三维的纳米结构.对纳米结构形成的机理进行了初步分析.     

Fabrication of densely packed titania nanosheet films on solid surface by use of Langmuir-Blodgett deposition method without amphiphilic additives

Densely packed exfoliated nanosheet films such as Ti0.91O2, Ti0.8M0.2O2 (M = Co, Ni), Ti0.6Fe0.4O2, and Ca2Nb3O10 on solid substrates were prepared by the LB transfer method without any amphiphilic additives at the air-water interface. Nanosheet crystallites covered nearly 95% on the solid surface with minimum overlapping of nanosheets. The LB transfer method of the Ti0.91O2 nanosheet monolayer film is applicable for not only hydrophilic substrates such as quartz, silicon, indium-tin oxide (ITO), and glass but also the hydrophobic Au surface. On the basis of these points, the LB transfer method has advantages compared to the alternating layer-by-layer method, which makes use of oppositely charged polyelectrolytes such as poly(ethylenimine) (PEI). Adsorption of hydrophobic Ti0.91O2 nanosheets at the air-water interface is responsible for this LB transfer deposition method. The addition of tetrabutylammonium bromide into the subphase assisted the adsorption, causing an increase in the adsorbed amount of Ti0.91O2 nanosheets at the air-water interface.     

Photo-induced structural changes of azobenzene Langmuir-Blodgett films

Structural changes of the Langmuir-Blodgett (LB) films of azobenzene accompanied by photoisomerization are described. First, photoisomerization is explained in terms of 'free volume'. In the polyion complex monolayers of amphiphiles having two azobenzene units at the air-water interface, the area per molecule depends on the polycation species. The fraction of cis-azobenzene in the LB films at the photostationary state under the illumination with UV light increased with increasing area per molecule, which is consistent with the concept of free volume. Second, a counter example of the concept of free volume is presented. Three-dimensional cone-shaped structures developed with trans-to-cis photoisomerization in the polyion complex LB film of a water-soluble amphiphilic azobenzene. These structures appeared and disappeared reversibly by alternate illumination with UV and visible light. The results indicate that the two-dimensional LB film structure exerts significant modification by photoisomerization. This is against the concept of free volume because this concept does not consider the possibility that the two-dimensional LB film structures may change into three-dimensional ones. Finally, photo-induced J-aggregate formation of non-photochromic and photochromic dyes is described. Two cyanine dyes were each mixed with an amphiphilic azobenzene in the LB films. These cyanine dyes are known to form J-aggregates in single-component LB films. In the mixed LB films, the J-aggregate formation was suppressed to some extent. The alternate illumination of the films with UV and visible light caused the photoisomerization of azobenzene in the mixed LB films, which triggered the J-aggregate formation of the cyanine dyes. The J-aggregate formation was accompanied by the development of three-dimensional cone-shaped structures from the film surface. When an amphiphilic merocyanine was mixed with the azobenzene in the LB films, J-aggregate formation was also induced by the alternate illumination with UV and visible light. This J-aggregate formation was also accompanied by a large morphological change: circular domains changed into fractal-like ones. The J-aggregate formation of the dyes and the concomitant morphological change were irreversible. In these cases, the photoisomerization of azobenzene served as a trigger to induce self-organization of the dye molecules.     

一种含苯并菲侧基的“毛-棒”状梯形聚倍半硅氧烷LB膜研究(英文)

一种新的含烷基取代的苯并菲侧基的"毛-棒"状(hairy-rod)梯形聚倍半硅氧烷(LPSQ)可以在空气-水界面形成稳定的单分子层,研究了温度、铺展溶剂和浓度对π-A等温曲线的影响.在适当的表面压下,以甲苯为铺展溶剂该单分子层可以被成功地转移至疏水的硅片或石英片上形成均一稳定的Y-型LB膜,其紫外吸收强度在几个月内均保持不变,说明该LB膜具有良好的稳定性,AFM图像表明其形成了均一致密的膜.通过偏振紫外光谱和荧光光谱研究了其面内各向异性,发现LPSQ的分子链采取了平行于拉膜方向的优先取向,最优取向因子S为0.42.     

Supramolecular assembly at interfaces: formation of an extended two-dimensional coordinate covalent square grid network at the air-water interface

Reaction of a Langmuir monolayer of an amphiphilic pentacyanoferrate(3+) complex with Ni(2+) ions from the subphase results in the formation of a two-dimensional iron-nickel cyanide-bridged network at the air-water interface. The network can be transferred to various supports to form monolayer or multilayer lamellar films by the Langmuir-Blodgett (LB) technique. The same network does not form from homogeneous reaction conditions. Therefore, the results demonstrate the potential utility of an interface as a structure director in the assembly of low dimensional coordinate covalent network solids. Characterization of the LB film extended networks by X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, SQUID magnetometry, X-ray absorption fine structure (XAFS), and grazing incidence synchrotron X-ray diffraction (GIXD) revealed a face-centered square grid structure with an average domain size of 3600 A(2). Magnetic measurements indicated that the network undergoes a transition to a ferromagnetic state below a T(c) of 8 K.     

Structures of palmitoyl-L and DL-lysine monolayers at the air-water interface--polarization modulation infrared reflection absorption spectroscopic study

Polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) was applied to measure the IR spectra of palmitoyl-DL-lysine (L-PL) and palmitoyl-DL-lysine (DL-PL) at the air-water interface. The spectra in the amide I and II regions were simulated by using the extinction coefficients of the amide I and II bands of L-PL and DL-PL determined by the analyses of the IR external reflection spectra of the Langmuir-Blodget (LB) films prepared on a Ge plate (Yasukawa et al. J. Mol. Struct. 2005, 735-736, 53), indicating the angle between the plane of the secondary amide group (the amide plane) and the surface normal in the L-PL monolayer to be about 20 degrees and the angle in the DL-PL monolayer to be about 37 degrees. Comparison of the tilt angles with the corresponding angles in the LB films (about 20 degrees for the LB film of L-PL; about 49 degrees for the LB film of DL-PL) indicated that, upon being transferred to the solid substrate from the air-water interface, the L-PL monolayer keeps the orientation of the amide plane virtually unchanged, while the DL-PL monolayer changes the orientation appreciably to a horizontal direction. The orientation change of the amide plane was interpreted as due to the accommodation of irregularly oriented palmitoyl groups into the LB films of DL-PL on the solid substrate.     

Luminescent Langmuir-Blodgett films of platinum(II) complex [Pt(L18)Cl](PF6) (L18 = 2,6-bis(1-octadecylbenzimidazol-2-yl)pyridine)

A novel amphiphilic Pt complex containing 2,6-bis(1-octadecylbenzimidazol-2-yl)pyridine (L18), [Pt(L18)Cl](PF6), has been synthesized. The complex exhibits concentration-dependent absorption and emission spectra in solution. With increasing the concentration of the Pt complex, we observed a new absorption band centered at 550 nm derived from a metal-metal d sigma* to ligand pi* charge transfer (MMLCT) transition and the corresponding broad emission centered at 650 nm. The Pt complex is surface-active, and the surface pressure-area isotherm reveals three phase transitions. The three phases correspond to one liquid-expanding phase and two solid-condensed phases, respectively, with different intermolecular overlap in the "flat-on" orientation at the air-water interface. Without additives such as fatty acids, the complex forms a stable and reproducible Langmuir-Blodgett (LB) multilayer film above a surface pressure of 15 mN m-1. Strong emission from the LB films, even monolayer, was observed. Comparing the relative emission intensity of the MMLCT band for transferred LB monolayer film with that for cast films, we concluded that Pt-Pt interactions are suppressed in the LB film. Instead, the emission at 600 nm arising from the ligand-ligand pi-pi interacted excited state became dominant. The results would provide the insight into the control of molecular ordering for planar Pt complexes from the viewpoint of characteristic excited states.     

Langmuir-Blodgett films of a cationic zinc porphyrin-imidazole-functionalized fullerene dyad: formation and photoelectrochemical studies

Electron donor-acceptor dyad ensembles of a water-soluble cationic zinc porphyrin (viz., zinc tetrakis(N-methylpyridinium)porphyrin tetrachloride, Zn(TMPyP)) and a C60 derivative that bears an imidazole ligand (viz., 2-(phenylimidazolyl)fulleropyrrolidine, C60im) were assembled during the formation of Langmuir and then Langmuir-Blodgett (LB) films. Surface pressure versus surface area isotherms and surface pressure time profiles, as well as Brewster angle microscopic images documented that the Langmuir films formed were remarkably stable. Subsequently, these Langmuir films were transferred onto different solid substrates, by using the LB technique, for spectroscopic and photoelectrochemical characterization. The UV-vis spectroscopic investigations confirmed that the water-soluble Zn(TMPyP) was, indeed, transferred together with C60im in the LB films. Upon visible light illumination of these LB films, deposited on the ITO transparent conductive supports, a photocurrent generated in the C60im-Zn(TMPyP) system is ascribed to an efficient photoinduced electron transfer from the electron donor, porphyrin singlet excited-state to the electron acceptor, C60. Overall, internal photon-to-current efficiency, IPCE, of the photoanodic current generation (with ascorbate as a sacrificial electron donor) in the ITO/C60im-Zn(TMPyP)/ascorbate/Pt construct is over 5x larger than that of the photocathodic system (with methyl viologen, MV2+, as a sacrificial electron acceptor) in the ITO/Zn(TMPyP)-C60im/MV2+/Pt construct. Highly ordered film stacking favors vectorial electron transfer within the dyad, giving rise to the highest IPCE values of 2.5% determined for a photoanode that was composed of around 20 monolayer films.     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

Phase-separation of mixed surfactant monolayers: a comparison of film morphology at the solid-air and liquid-air interfaces

The morphologies of phase-separated monolayer films prepared from two different binary mixtures of perfluorocarbons and hydrocarbons have been examined and compared, for the first time, at the solid-air and liquid-air interfaces. Films were comprised of binary mixtures of arachidic acid (C(19)H(39)COOH) with perfluorotetradecanoic acid (C(13)F(27)COOH) and of palmitic acid (C(15)H(31)COOH) with perfluorooctadecanoic acid (C(17)F(35)COOH). For both mixed systems, Langmuir Blodgett films on mica substrates consisted of polygonal domains of one surfactant dispersed in a continuous matrix of the other (arachidic acid in perfluorotetradecanoic acid or perfluorooctadecanoic acid in palmitic acid, respectively), consistent with previous reports. Real-time imaging of the air-water interface via Brewster angle microscopy revealed that comparable film morphology was present at the air-water interface and the solid-air interface over a wide range of surface pressures, and that for the arachidic acid-based mixture, domain growth dynamics at the air-water interface is consistent with that inferred from sequential "static" atomic force microscope images collected at the solid-air interface.     

Conformational changes of a calix[8]arene derivative at the air-water interface

The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules.