不同取代基的噻碳菁和吲哚碳菁染料对其在溴化银微晶上吸附能力及形成J-聚集体尺寸分布的影响

本文研究了5-位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和T-颗粒溴化银微晶上吸附能力的影响,并采用ACFEM(Analytical Color Fluore scence Electron Microscopy)研究了上述结构染料对其吸附在溴化银微晶所形成的J-聚集体尺寸分布的影响。实验结果表明,对吲哚碳菁染料来说,立方体溴化银微晶表面的吸附能力较T-颗粒溴化银微晶表面的吸附能力强;但对噻碳菁染料来说则相反,它们在T-颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强。另外,对5-位不同取代基的噻碳菁染料而言,无论是在立方型颗粒或T-颗粒溴化银微晶上的吸附能力来说,含取代基(无论4-取代基是吸电子型还是推电子型)的噻碳菁染料较未取代的噻碳菁染料强;而5-位取代基是吸电子型的噻碳菁染料更有利于其吸附在T-颗粒溴化银微晶表面。此外,本文还进一步证明了溴化银微晶表面上染料J-聚集体的生长过程是符合奥斯瓦尔特成熟过程的。吲哚碳菁染料在T-颗粒溴化银微晶上形成的J-聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的J-聚集体的平均尺寸。吸附在立方体溴化银微晶上的5-不同取代基的噻碳菁染料对其形成J-聚集体尺寸分布的影响的研究结果表明,含取代基(-CH₃,-Ph,-Cl)的噻碳菁染料形成的J-聚集体的尺寸分布几乎相同,但与未取代的噻碳菁染料形成的J-聚集体的尺寸分布明显不同;5-位含取代基的噻碳菁染料形成的J-聚集体平均尺寸大于未取代的噻碳菁染料的。     

Effects of NaCl on the J-aggregation of two thiacarbocyanine dyes in aqueous solutions

The effects of NaCl on the aggregation of two typical thiacarbocyanine dyes (3,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzo-9-phenyl-thiacarbocyanine triethyl ammonium salt (Dye 1) and 3,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzo-9-methyl-thiacarbocyanine triethyl ammonium salt (Dye 2)) in aqueous solution have been studied by using absorption spectroscopy, fluorescence spectroscopy, and 1H- and 23Na-NMR measurements. It is found that the J-aggregation of two dyes can be promoted by the addition of NaCl and that the effective coherence length of the J-aggregate is shorter than that obtained without NaCl. Fluorescence spectra demonstrate that the fluorescence intensities of the J-aggregates of two dyes are quenched by addition of NaCl. This is consistent with the decrease of the effective coherence length of J-aggregates of the two dyes in the presence of NaCl. 1H-NMR spectra of two dyes show that the Na(+) ions penetrate into the J-aggregates and replace the counterion (triethylammonium ions) in two dyes. The measurements of the chemical shifts of 23Na nuclei provide further information about the interaction between the Na(+) ions and dye anions in the J-aggregates of the two dyes. Due to this interaction, the electrostatic repulsion between the dye anions in the J-aggregates can be reduced and thus accelerate the aggregation of the two dyes in the presence of NaCl. The apparent association constants between Na(+) ions and dye molecules in J-aggregates of Dye 1 and Dye 2 estimated from the measured chemical shifts of 23Na nuclei are about 2.38 M(-1) and 1.35 M(-1), respectively.     

Determination of the dimerization constant of pinacyanol: role of the thermochromic effect

Pinacyanol (PIN), as other cyanine dyes, has demonstrated a unique ability to form associates such as dimers, and H- and J-aggregates. This association is strongly favoured in water, and even at low dye concentrations, dimers and superior order aggregates are present. As a consequence, the determination of the dimerization constant involves sometimes a significant error when these aggregates are neglected. As an increase in temperature shifts the equilibrium among the different species towards the lowest order aggregates, we have obtained the spectra of PIN at several temperatures. By extrapolating some spectral characteristics at high temperatures, a spectrum of the dimer without any contribution of other aggregates was obtained. From this spectrum and that of the monomer, the dimerization constant was calculated, as well as the Gibbs energy change associated to the reaction. The enthalpy and entropy changes of the dimerization were determined from the dependence of the dimerization constants on the temperature. From these results it can be inferred that the driving force of the dimerization is of enthalpic origin.     

Fundamental Aspects of Xanthene Dye Aggregation on the Surfaces of Nanocluster Polyoxometalates: H- to J-Aggregate Switching

The induced aggregation of the xanthene dye rhodamine B (RhB) on metal oxide centers belonging to the highly symmetric surfaces of precise nanoscale templates with Keplerate (Mo₁₃₂) or toroidal (Mo₁₃₈) structures has been studied. With the joint use of the Langmuir isotherm and full Stern–Volmer models, the thermodynamic reasons for dye adsorption on the nanocluster surface, such as a mixture of monomer, H-aggregate (H-dimer), and J-aggregate forms (which can coexist or switch one into another under the exact conditions), were established: this was shown through UV/Vis and fluorescence spectroscopies. By using the framework of the exciton model, it is shown that the angle (α) between the transition dipole moments of RhB is very sensitive to surface strain inside the dye sub-monolayer. As a result, it is possible to switch from H- to J-aggregates by the post-functionalization of polyoxometalate (POM)-RhB associates by the surfactant bilayer shell, which allows the surface strain to grow. Recommendations are provided for managing the appearance of H- or J-aggregates on metal oxide (or polyelectrolyte) surfaces during photovoltaic or bioimaging applications.     

Kinetics of salt-induced J-aggregation of cyanine dyes

The addition of monovalent, divalent, and trivalent metal ions to three anionic ethyl meso-thiacarbocyanine dyes, an ethyl meso-oxacarbocyanine, and an imidacarbocyanine in aqueous solution at room temperature results in the production of J-aggregates within the range of tens to hundreds of seconds. The rate of formation of J-aggregates correlates with the rate of decay of dimers or monomers and is dependent on the type of metal ion, dye structure, and temperature. The rate of formation of J-aggregates increases as the temperature decreases and the dye and salt concentrations increase, and the rate is highest for trivalent ions and smallest for monovalent ions, independent of the type of anion. The time course of formation of J-aggregates is described in most cases by a sigmoidal curve, and the kinetics and mechanism are discussed within the framework of autocatalysis. Computer simulations reveal that the sigmoidal time dependence is transferred to an exponential-like curve by substantially increasing the rate constant for the noncatalytic step. The reaction pathway into J-aggregates can be switched from dimeric ion pairs as the reactant to monomeric ion pairs, when the rate constant for the catalytic step via the monomer becomes larger with respect to that via the dimer.     

The role of cellulose acetate as a matrix for aggregation of pseudoisocyanine iodide: absorption and emission studies

Films of pseudoisocyanine iodide in a cellulose acetate matrix were prepared by spin coating and characterized by UV/Vis absorption and fluorescence spectroscopies. The comparison with self-supported films of the same dye enabled analysing the role of the matrix in the aggregation of pseudoisocyanine iodide ([PIC]I). It was proved that cellulose acetate is a suitable support for [PIC]I J-aggregates, which form during spinning, as shown by a very sharp J-band in the absorption spectra. This indicates a perfect coherence between stacked monomers in the supported J-aggregates. It was possible to individualize the emission spectrum of [PIC]I J-aggregates in cellulose acetate, by decomposition of the steady-state fluorescence spectra of the films. The dependence on the excitation wavelength of the relative emission intensities of monomers and J-aggregates, for lambda(em) = 587 nm, lead to confirm that the latter species have an absorption maximum at approximately 500 nm in cellulose acetate. Finally, polarised absorption spectra of films obtained by the vertical spin coating technique showed that cellulose acetate allows a partial orientation of J-aggregates.     

Multi-electron transfer reactions and exciton interactions in fibrous porphyrin and metalloporphyrin assemblies

Non-covalent porphyrin and metalloporphyrin fibers of bimolecular thinness in bulk aqueous media are compared with the well-known H- and J-aggregates of cyanines. The J-aggregates of cyanines fluoresce and are useful as photographic sensitizers. The J-aggregates of porphyrins show light-induced charge separation and the corresponding metal complexes produce stable radical dimers. The distance between the metalloporphyrin centers is calculated from circular dichroism spectra to be 8 Å in the J-aggregates and about 4 Å in the H-aggregates. Multi-electron reactions of the fibers in the ground and excited states can therefore occur in the fibrous porphyrin assemblies. In amphiphilic tetraphenylporphyrins (“octopus porphyrin”), on the other hand, the porphyrin–porphyrin distance is much larger and the fiber dissolves electron-accepting compounds, e.g. quinones, which also allow for multiple charge separation within such a fiber.     

J-aggregation in alpha-sexithiophene submonolayer films on silicon dioxide

We report on the observation of J-aggregates in submonolayer films of alpha-sexithiophene grown on silicon dioxide. Photoluminescence spectroscopy reveals that submonolayers are formed by molecules lying flat on the substrate with a head to tail configuration. Excitation energy dependence of photoluminescence shows a red-shifted absorption with respect to isolated molecules and a negligible Stokes shift between absorption and emission. The pronounced structural order of J-aggregates is reflected in the fwhm of the emission bands. From time-resolved and low-temperature photoluminescence experiments, we infer a quantum yield of the J-aggregate between 0.6 and 1. The demonstration of spontaneous formation of J-aggregates of pi-conjugated systems on amorphous silicon-based substrates can be relevant for the development of organic-inorganic hybrid photonic devices.     

Controlled formation of the two-dimensional TTBC J-aggregates in an aqueous solution

Strong experimental and theoretical evidence was provided on the controlled formation of the two-dimensional J-aggregates that were assembled in the herringbone morphology. The exciton-band structure formation of 1,1',3,3'-tetraethyl-5,5',6,6'-tetrachlorobenzimidazolocarbocyanine (TTBC) J-aggregates was investigated in ionic (NaOH) aqueous solution at room temperature. The control was achieved by changing the [TTBC] at a given [NaOH], or vice versa, and was monitored through the changes in the absorption, fluorescence excitation, and emission spectra. Specific attention was paid to expose the excited-state structure and dynamics through simulations of the excitonic properties, which included diagonal energetic disorder and phonon-assisted exciton relaxation. Aggregates were characterized by an asymmetrically split Davydov pair, an H-band (approximately 500 nm, 1300 cm(-1) wide, Lorentzian-like) and a J-band (approximately 590 nm, 235 cm(-1) wide, with a band shape typical of a one-dimensional J-aggregate), whose relative intensities showed a strong dependence on the [TTBC]/[NaOH]. The H-band is favored by high [TTBC] or high [NaOH]. An explanation of the control on the aggregate formation was given by correlating the changes in the absorption with the structural modifications and the subsequent changes in the dynamics, which were induced by variations in the dye and NaOH concentrations. The J-band shape/width was attributed to disorder and disorder-induced intraband phonon-assisted exciton relaxation. The intraband processes in both bands were estimated to occur in the same time scale (about a picosecond). It has been suggested that the wide energetic gap between the Davydov split bands (3000 cm(-1)) could get bridged by the excitonic states of the loosely coupled chains, in addition to the monomeric species at low [TTBC]. Phonon-assisted interband relaxation, through the band gap states and/or directly from the H- to the J-band, are suggested for accounting the difference between the bandwidths and shapes of the two bands. Energy transfer between the H-band and the monomeric species is suggested as crucial for tuning the relative strengths of the two bands.     

Experimental and theoretical study on molecular aggregation and its effect on the photo-physical properties of the mesogenic bi-1,3,4-thiadiazole derivative

A bi-thiadiazole derivative, 5,5'-bis(4- tetradecyloxyphenyl)-2,2'-bi-1,3,4-thiadiazole (BTD-14), was revealed to exhibit an extremely stable thermotropic SmC phase and very interesting aggregation behavior in solutions. H- and J-aggregates could be formed simultaneously in chloroform solutions of BTD-14 with moderate concentration (10(-4) M), and the population of J-aggregates enlarges during further concentration increase. All monomers, H-aggregates and J-aggregates in solutions could be reserved in the drop-cast films, and both the presence of J-aggregates and the energy transfer path from H-aggregates to J-aggregates were considered to contribute to the relative high solid state fluorescence quantum yield (33%). The BTD-1 dimer potential energy surface (PES) was computed with M062x/6-31G** method, and the molecular packing pattern corresponding to the lowest minimum of the PES are in good agreement with the crystal structures. Exploring the effect of molecular packing on its electronic structure with the TD-M062x method revealed that J-aggregates could be formed by enlarging the intermolecular displacement along the molecular long axis by about 9.8 ?.     

Langmuir-Blodgett单分子膜功能体系的研究(Ⅲ).有序单分子膜内的J-聚体

本文讨论了单分子膜内J-聚体的性质、稳定性以及影响J-聚体形成的因素。实验中发现,制备有序单分子膜时,机械振动是影响J-聚体形成的重要因素;利用分子的电性质,靠外加电场的作用,可以增加J-聚体的成份。载于玻璃载片上单分子膜中的J-聚体在室温下就可以破坏,在低温下能够得以保存。根据J-聚体的能级性质及其在能量转移中的作用,作者认为,J-聚体可以形成激子态,J-聚体内的能量转移是激子转移。     

Photophysical property and photostability of J-aggregate thin films of thiacyanine dyes prepared by the spin-coating method

By use of electrostatic interactions of dye molecules and poly(diallyldimethylammonium chloride) (PDDA), the spin-coating technique has been successfully applied to the preparation of stable J-aggregate thin films of thiacarbocyanine dyes on a polycarbonate or quartz plate. The J-aggregate thin films were prepared by the spin-coating of PDDA aqueous solution on dye thin films prepared on a substrate by the spin-coating of 2,2,3,3-tetrafluoro-1-propanol solution of dyes. Photophysical properties of the dye thin films and J-aggregate thin films were studied by measuring the fluorescence spectra, quantum yields, and lifetimes. Coherent size of the J-aggregates was estimated to be 3-12 by means of the absorption bandwidth (full width at half maximum) or radiative lifetime. Photostability of the J-aggregate thin films was also studied in terms of photodegradation efficiency under argon and oxygen in comparison with the dye thin films, and J-aggregate thin films were found to be more stable than the corresponding dye thin films.     

Spectral properties of rhodamine 3B adsorbed on the surface of montmorillonites with variable layer charge

Montmorillonite was thermally treated at several temperatures to reduce the charge density of its layer surface. Absorption and fluorescence (steady-state and time-resolved) spectroscopies are now applied to study the adsorption of rhodamine 3B (R3B) laser dye in reduced charge montmorillonites (RCMs) in aqueous suspensions. The decrease in the charge density increases the intermolecular distance between adsorbed R3B molecules, reducing the tendency of the dye to self-associate. H-type and J-type aggregates of R3B in RCMs are spectroscopically characterized, the fluorescent J-aggregates being more extensively formed by decreasing the charge density. Both the reduction in the dye aggregation and the formation of J-type aggregates enhance the fluorescence efficiency of R3B dye adsorbed in montmorillonite particles. Absorption with linearly polarized light reveals that the H-aggregates are more disposed toward the perpendicular of the clay surface than the monomer and J-aggregates species.     

Photorefractive Properties of a Polyimide Containing Thiacarbocyanine Dye J-Aggregates

The photorefractive properties of a polyimide containing J-aggregates of a thiacarbocyanine dye were examined. Measurements were made with a holographic apparatus at Ar–Kr laser wavelengths of 647 and 514 nm. The J-aggregate and the monomeric form of the dye, respectively, are responsible for the photoelectric sensitivity at these wavelengths. It was shown that the J-aggregates are also responsible for the nonlinear optical properties of the polymeric system. The combination of these features determines the photorefractive characteristics of the polymer composite: under interference conditions, the intensity of one of the interacting beams (signal beam) increases at the expense of extinction of the other (pumping) beam. The difference between the beam-coupling gain coefficient and the absorption coefficient increases at 647 nm from 217 to 361 cm^–1 with the increasing strength of a constant electric field E ₀ applied to the layer from 16 to 123 V/m. Only the samples containing J-aggregates display the photorefractive effect at 514 nm.     

Contrasting behavior of classical salts versus ionic liquids toward aqueous phase J-aggregate dissociation of a cyanine dye

The effect of addition of ionic liquids (ILs) on the aggregation behavior of a cyanine dye, 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC), was investigated. In basic aqueous buffer solutions (pH ≥ 10), TDBC preferably exists in its J-aggregated form. Addition of hydrophilic ILs > 5 wt % is observed to disrupt the TDBC J-aggregates, converting them to monomer form most likely because of the interaction between bulky IL cation and the J-aggregates in a time-dependent fashion. This is evidenced by the observed increase in monomer band absorbance at the expense of the absorbance band due to J-aggregates over time. Inorganic salts at similar molar concentrations do not cause this phenomenon but instead induce TDBC precipitation. At low concentrations (<5 wt %), the added IL acts similarly to the inorganic salts, reducing the overall absorbance of TDBC in the solution most likely due to cation exchange causing TDBC precipitation. Addition of a molecular solvent, ethanol, at 15 wt % results in an initial increase in monomer absorbance, albeit to a much lesser extent than for the corresponding molar fraction of IL, which then decreases over time with recovery of J-aggregate absorbance--quite opposite the time-dependent behavior seen for TDBC in PB at pH 12.0 with >5 wt % IL. The unique and dual behavior of ILs as an additive toward affecting cyanine dye aggregation is demonstrated.     

四苯基卟啉锌J-聚集体的光谱与晶体结构分析

四苯基卟啉锌在完全无水的乙氰中发生自聚现象, 聚集体的形成可以通过稳态光谱来证实. 吸收光谱和荧光发射光谱的红移表明四苯基卟啉锌的聚集体是卟啉之间以头对头的方式排列, 即J-聚集体. 进一步研究表明聚集体的形成还依赖于溶剂. 光谱和激发态寿命的测定结果表明聚集体的辐射跃迁速率比单体快两倍, 这表明形成的J-聚集体存在超辐射. 四苯基卟啉锌的晶体呈现出杆状的结构. 通过X射线的结构分析, 提出了一个四苯基卟啉锌J-聚集体的结构模型. 四苯基卟啉锌中的一个苯基和相邻的四苯基卟啉锌中的吡咯垂直并通过C—H…π键相互作用. 最后讨论了乙氰配位后对四苯基卟啉锌中Zn—N键的影响.     

Infrared Spectroscopic Investigations of J-aggregates of Protonated Tetraphenylporphine

Protonated tetraphenylporphine(H2TPP) J-aggregates were prepared by aggregation on the liquid-air interface,Using FTIR spectroscopy,the authors observed the infrared absorption spectra of H2TPP and its J-aggregates.The IR spectra of H2TPP J-aggregates show significant changes compared with that of H2TPP monomer.Intensity changes(e.g.,strong enhancement of the in-plane vibronic mode and weakening of the out-of-plane vibronic mode of phenyi and porphyrin skeletal) were interpreted on the basis of stacking effects.Observation of the same type of bands collapse into single band was explained by the increase in the symmetry of H2TPP molecules.And the new bands at 1635 and 3407 cm-1 indicate the aggregates containing a large amount of bound water.     

J-aggregation and disaggregation of indocyanine green in water

J-aggregates of indocyanine green sodium iodide in water are formed by heat treatment. Starting from a dimeric solution the activation energy of molecule attachment (E_att ≈ 0.41 ev) to J-aggregates is determined by analysing the temperature dependence of the rate of J-aggregate absorption growth. The activation energy of molecule detachment (E_det ≈ 0.51 eV) from J-aggregates is deduced from the temperature dependent rate of J-aggregate absorption decrease after strong dilution.     

Exciton-coupled charge-transfer dynamics in a porphyrin J-aggregate/TiO(2) complex

Exciton-coupled charge-transfer (CT) dynamics in TiO(2) nanoparticles (NP) sensitized with porphyrin J-aggregates has been studied by femtosecond time-resolved transient absorption spectroscopy. J-aggregates of 5,10,15-triphenyl-20-(3,4-dihydroxyphenyl) porphyrin (TPPcat) form CT complexes on TiO(2) NP surfaces. Catechol-mediated strong CT coupling between J-aggregate and TiO(2) NP facilitates interfacial exciton dissociation for electron injection into the conduction band of the TiO(2) nanoparticle in pulse width limited time (<80 fs). Here, the electron-transfer (<80 fs) process dominates over the intrinsic exciton-relaxation process (J-aggregates: ca. 200 fs) on account of exciton-coupled CT interaction. The parent hole on J-aggregates is delocalized through J-aggregate excitonic coherence. As a result, holes immobilized on J-aggregates are spatially less accessible to electrons injected into TiO(2) , and thus the back electron transfer (BET) process is slower than that of the monomer/TiO(2) system. The J-aggregate/porphyrin system shows exciton spectral and temporal properties for better charge separation in strongly coupled composite systems.     

Porphyrin J-aggregates stabilized by ferric myoglobin in neutral aqueous solution

J-aggregates of a diacid form (H4TPPS2-) of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4-) were stabilized by binding with ferric myoglobin (metMb) in aqueous solution at neutral pH. The J-aggregates gradually dissociated to monomeric H2TPPS(4-). The average half-lifetime (t1/2) of the J-aggregates in the presence of sufficient amounts of metMb was ca. 3 h in phosphate buffer at pH 7.0 and 25 degrees C. The stabilization of the J-aggregate by metMb is ascribed to encapsulation and fixation of an edge-to-edge structure of the J-aggregate by the relatively rigid protein molecules. The secondary structure of metMb was altered in some extent in the presence of an excess amount of the J-aggregates while no effect on denaturation of metMb was observed with the H2TPPS(4-) monomer or polyacrylate. The hydrophobic nature of the J-aggregate seems to play an important role for denaturation of metMb. The ability of denatured metMb to bind the azide anion was higher than that of natural metMb. The denaturation of metMb by the J-aggregates seems to induce surfacing of hemin leading to an entropy gain in coordination of the N3(-) anion to the iron(III) center.