Aggregation Of Chromophores Research Articles

Photocontrol of chiroptical properties of polydiacetylene carrying azobenzene in the side chain

We study azobenzene-substituted diacetylene (PADA)/poly(methyl methacrylate) (PMMA) hybrid films that are pertinent to the problem of mirror symmetry breaking induced by circularly polarized UV light (CPUL). The morphology and packing structure of the resulting hybrid films were characterized by AFM and XRD. Striking CD signals for azobenzene chromophores and polydiacetylene chains were observed in the resulting polymerized PADA/PMMA hybrid films irradiated with left- or right-handed CPUL. Influence of the aggregation and orientation of azobenzene chromophores on the photoinduced chiroptical properties was analyzed in detail. Further, the effects of annealing treatment on photoinduced chirality of the hybrid films were studied.

New progress in aggregation-induced emission research

The most fascinating aspect of scientific research is the constant deciphering of mysterious puzzles and the continuous transformation of our mode of thinking. While textbook knowledge is the foundation of human wisdom, some traditional concepts can later prove to be imperfect or even incorrect owing to limitations of the observations and understanding of the involved natural phenomena in particular periods of history. The once popular “geocentric theory”, for example, was totally wrong and hampered scientists’ exploration of the universe, and the “vitality of the doctrine” badly hindered advancement in organic chemistry research. Innovations are needed to break the restraints of such traditional concepts. The area of organic solids research focuses on investigations of molecular functional materials with peculiar optical, electronic and magnetic properties. In this area, a generally accepted concept is that chromophore aggregation always leads to luminescence quenching. This phenomenon of aggregation-caused quenching (ACQ) is termed the “concentration-quenching effect” in the textbook Molecular Fluorescence. Researchers are working on the development of organic light-emitting diodes (OLEDs), in which luminescent molecules are used as a solid film, one of the aggregation forms. Scientists have tried hard to suppress the aggregate formation of luminescent molecules through different approaches, with the aim of mitigating the ACQ effect and achieving OLEDs with high efficiencies. In 2001, Tang’s group discovered a phenomenon exactly opposite to the ACQ effect. The researchers found that luminogen aggregation played a constructive, instead of destructive, role in the light-emitting process; a series of silole molecules, such as hexaphenylsilole (HPS) and methylpentaphenylsilole (MPPS; Figure 1), were found to be nonluminescent in the solution state but emissive in the aggregated state with luminescent quantum yields three orders of

Novel hybrid photosensitizers: Photoactive polymer–nanoclay

A new type of hybrid photosensitizers was obtained by efficient adsorption of a photoactive polymer by an organically modified nanoclay. The polymer bore naphthyl and rose bengal chromophores, which absorbed light both in the ultraviolet and visible spectral region. Adsorption of the polymer on nanoclay prevented aggregation of chromophores. The obtained hybrid photosensitizer efficiently adsorbs hydrophobic compounds. It was also found to be an efficient photosensitizer in singlet oxygen generation. The hybrid photosensitizers combine the advantages of both component systems, i.e. possibility to attach a wide range of chromophores to the polymeric chain and resulting ability to photosensitize reactions, on one hand, and the ability to adsorb hydrophobic pollutants and easy separation from water characteristic of nanoclays, on the other.

Control of the Aggregation of a Phenylenevinylenediimide Chromophore by Use of Supramolecular Chemistry: Enhanced Electroluminescence in Supramolecular Organic Devices

A new approach toward the tuning of the supramolecular organization of π-conjugated substructures containing imide functional groups has been investigated using the concept of supramolecular chemistry. This approach, which allows enhanced emission properties of the active material, was evaluated in the fabrication of optoelectronic devices. A linear ditopic chromophore H-ImPV was synthesized. This N−H imide constitutes a recognizing unit with an acceptor−donor−acceptor (ADA) hydrogen bond motif. End-capping of this new chromophore with a monotopic structuring unit allowed control of the supramolecular aggregation of the π-conjugated chromophore. The studies of the absorption and emission properties of the H-ImPV, in solution or in the solid state (thin films, powders), clearly revealed different aggregation behaviors, depending on the presence of the monotopic structuring unit: hindered unit (Cy-DAT) led to the formation of J-aggregates. In all cases, evidence for the heteromolecular association H-ImPV· ·...

Exciton coherence length fluctuations in chromophore aggregates probed by multidimensional optical spectroscopy

The coherent third order optical response of molecular aggregates with fluctuating frequencies, couplings, and transition dipole moments is studied. We derived stochastic nonlinear exciton equations (SNEEs) by combining the quasiparticle picture of excitons with the path integral over stochastic bath paths described by the stochastic Liouville equations. Coherent two-dimensional (2D) spectra are calculated for a tetramer model system whose transition dipole orientations undergo two-state stochastic jumps on an arbitrary timescale. Correspondence between domains of ordered dipoles, which determine the exciton coherence length and the absorption peaks, is established. Signatures of domain coherence length fluctuations are observed in the cross peak dynamics of the 2D spectra in specific pulse polarization configurations.

Solvent Effects on Structure, Morphology, and Photophysical Properties of an Azo Chromophore-Functionalized Polydiacetylene

We investigate the effects of solvents on structure, morphology and photophysical properties of micelle-like assemblies of an azo chromophore-functionalized polydiacetylene (polyAzoDA) and polymerized tricosa-10,12-diynoic acid (polyTDA) for comparison. Using mixtures of water with glycol, DMSO, ethanol and THF, we systematically vary the solubility parameters and observe blue-to-red color changes of polydiacetylenes. Teas plots are used to estimate the strength of polymer−solvent interactions and explain the properties of polyAzoDA supramolecular assemblies in different solvent environments. In poor solvents, polyAzoDA forms rod-like micelles and the photoisomerization is strongly hindered by the aggregation of azo chromophores. At increasing content of organic solvents, polyAzoDA becomes gradually swollen, as indicated by the onsets of blue-to-red color changes, starting trans−cis isomerizations of the azo groups, and changes of the structures as seen in SEM images. At large ethanol content, we observe that photoisomerization of azobenzene groups induces a morphological transition and a color change of the polydiacetylene backbone.

High and stable photoinduced anisotropy in guest–host polymer mediated by chromophore aggregation

We present a novel materials concept for optical inscription of stable birefringent optical elements into guest-host type polymers by making use of chromophore aggregation. The method is based on photoalignment of azobenzene chromophores, the aggregation of which leads to significant enhancement and stabilization of the photoinduced birefringence. The obtained order parameter of the molecular alignment (0.3) in combination with the exceptional thermal stability of the anisotropy renders the material system unique among amorphous azobenzene-containing polymers and provides a route toward designing efficient photoresponsive optical elements through the guest-host type approach.

Photoswitchable Intramolecular H-Stacking of Perylenebisimide

Dynamic control over the formation of H- or J-type aggregates of chromophores is of fundamental importance for developing responsive organic optoelectronic materials. In this study, the first example of photoswitching between a nonstacked and an intramolecularly H-stacked arrangement of perylenebisimides (PBI) is demonstrated. The system is composed of a central switching unit (overcrowded alkene) tethered to two PBI chromophores. cis-trans isomerization of the switching unit, induced by alternate irradiation at 312 and 365 nm, can drive two PBI chromophores reversibly between an intramolecularly "aggregated" and "nonaggregated" state. Distinct changes in UV-vis absorption and fluorescence spectra are observed following photoisomerization. This approach allows for efficient control of intramolecular H-stack formation with no significant intermolecular interactions spanning over at least 4 orders of magnitude of concentration (from 10(-8) to 10(-4) M) and a range of solvents and temperatures.

SUPPRESSION OF CHROMOPHORE AGGREGATION IN AMORPHOUS POLYMERIC MATERIALS: TOWARDS MORE EFFICIENT PHOTORESPONSIVE BEHAVIOR

We give an overview of our recent work on improving the optical performance of polymeric materials via supramolecular concepts, i.e., by making use of spontaneous non-covalent interactions between the chromophores and the polymer backbone. More precisely, we show that the aggregation of dipolar chromophores in amorphous polymeric materials can be controlled by simply choosing a proper polymer matrix. This approach has a potential impact in a wide range of optical phenomena where chromophore aggregation or phase separation sets a limit to the system performance.

Kinetics of phase separation in polymer blends revealed by resonance light scattering spectroscopy

In this work, kinetics of phase separation in the blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) was investigated by a simple and sensitive method, i.e., resonance light scattering (RLS) spectroscopy. Owing to the aggregation of chromophores (phenyl rings) in the systems when phase separation occurred, RLS intensities were drastically enhanced and hence acted as a characteristic indicator. At the early stage of phase separation, two different RLS behaviors corresponding to spinodal decomposition (SD) and nucleation and growth (NG) were observed. The Cahn-Hilliard (C-H) linearization theory was found not applicable for kinetics analysis of the scattering data at lambda < 346 nm due to RLS effect near the absorption band. Based on a decomposition reaction model, the apparent activation energy of SD phase separation was estimated by the Arrhenius equation. In view of its simplicity and sensitivity of measurement, affordability and availability of instrument, and wide application range of polymer blends, RLS proved to be an effective means for characterization of microstructural variation in polymer blends.

Novel Azobenzene-Functionalized Polyelectrolytes of Different Substituted Head Groups 1: Synthesis, Characterization and Absorption Spectroscopy Studies

A new class of a series of amphiphilic polyelectrolytes functionalized with azobenzene chromophores have been synthesized and thoroughly characterized by various techniques. A facile two stage strategy is developed, and first involved the preparation of a precursor base polymer, designated as P(APEA), by the free-radical copolymerization of the monomers of acrylic acid (AA) and 2-(phenylethylamino)ethyl acrylate (PEA). In the second step, precursor PAPEA polymers are reacted and post-polymer modified with the diazonium salts to synthesize azobenzene polyelectrolyte, PAPEA-R with different substituted R-groups present on the para position of the aromatic ring of the azo chromophores. The PAPEA-R polyelectrolytes are same in their degree of polymerization and repeat unit compositions of AA and PEA monomers, and only differ from each other by the type of R-groups. The copolymers were classified on the basis of the characteristics of their R-groups into the hydrophilic-ionizeable smaller pair of ─SO3H and ─COOH, the hydrophobic-non-ionizeable smaller pair of ─ H and ─OC2H5, and the hydrophobic-non-ionizeable larger octyl pair of ─C8H17 and ─ C8F17. The prepared copolymers are also characterized by NMR spectroscopy for structure, GPC for molecular weight, and UV-Visible spectroscopy for absorption determination. In DMF solvent, approximately similar absorption maxima, (λmax) values were observed for azo chromophore-containing monomers and after incorporating these into their corresponding polymers structures. However, for the self-assembled multilayer thin films, λmax moved to lower wavelengths to exhibit a blue shift with hydrophobic R-group of ─C8H17, while this behaviour was not observed for hydrophilic R-group of ─COOH. The shift in λmax is found to be highly dependent on the type of substituted R-group, and attributed to aggregation of hydrophobic azo chromophores in DMF:H2O mixture employed for self-assembly. The presence of the ionizeable AA and light-sensitive azo-chromophore functionalized PEA monomers in the PAPEA-R polyelectrolytes impart self-assembling and photoswitchable characteristics, respectively. Through understanding and controlling the solubility and complex solution aggregation behaviour of the different substituted R-groups of azo PEL, their adsorption, thickness, morphology, wetting, molecular-control, and photoresponsiveness can be tailored to enhance the capabilities of the self-assembled multilayer film process in diversified areas of microfluidics, sensing, and controlled release.

Aggregation-Induced Emission

Chromophore aggregation can quench emission, but it can also have the reverse effect by restricting intramolecular rotation. Several silole-based chromophores which exhibit this aggregation-induced emission (AIE) are presented here.

Effects of dilution with PMMA and network formation on fluorescence from benzimidazolylphenylenes linked to PMMA network

AbstractN,N′‐5‐(2‐benzimidazolyl)‐1,3‐phenylenebis(methacrylamide) (BIPBMA) was synthesized and copolymerized with methyl methacrylate (MMA) by changing feed BIPBMA/MMA molar ratio. The swelling experiments suggest that these cross‐linked copolymers (c‐copolymers) have a polymer network structure. To compare with c‐copolymers, synthesized 3‐(2‐benzimidazolyl) phenylmethacrylamide (BIPMA) was copolymerized with MMA by changing feed BIPMA/MMA molar ratio. These linear copolymers (l‐copolymers) were dissolved in N,N‐dimethylacetamide (DMA). The fluorescence spectra of c‐copolymers were well fitted by trial‐and‐error contraction with sums of five or less of Lorentzian equations. The fluorescence spectra of l‐copolymers were so distributed that only the initial peak was fitted to a single Lorentzian equation. The fluorescence spectra of BIPBMA/DMA solutions with various concentrations were also fitted to sums of five or less of Lorentzian equations. The fitted coefficients were used to quantify dilution effect. The fluorescence intensity of c‐copolymers is higher than that of l‐copolymers in a same chromophore concentration. A relation between the intensity and the chromophore concentration shows a concentration quenching owing to chromophore aggregating for c‐copolymer, l‐copolymer, and the solution. A critical concentration point before which the intensity increases appeared in the plots of intensity against concentration for the c‐copolymer and the solution. The critical point of the c‐copolymer is higher than that of the solution and that of the l‐copolymer (if observed). This suggests that the network formation and the dilution break up the chromophore aggregates. The fluorescence spectra of c‐copolymers (1/200) adjusted by varying AIBN concentrations suggest that the fluorescence is independent of the extent of cross‐linking. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Spectral Tuning of Organic Nanocolloids by Controlled Molecular Interactions

The controlled self-assembly of molecules and interactions between them remain a challenge in creating tunable and functional organic nanostructures. One class of molecular systems that has proven useful for incorporating tunable functionality at different length scales is liquid crystals (LCs) due to its ability to inherently self-organize. Here we present a novel approach to utilize the self-assembly of polymerizable liquid crystals to control the molecular aggregation of stable fluorescent chromophores and create a unique class of organic fluorescent nanocolloids. By adjusting the ratio between the dye and LC molecules inside the nanocolloids, we demonstrate the ability to control the molecular interactions and tune the fluorescent emission spectra of nanocolloid populations under single wavelength excitation. The single absorption spectrum and multiple emission spectra are highly desirable and reminiscent of the spectroscopic signature of quantum dots. These novel fluorescent nanocolloids have broad potential applications in fluorescent imaging and biological labeling.

An EFISH, Theoretical, and PGSE NMR Investigation on the Relevant Role of Aggregation on the Second Order Response in CHCl3 of the Push−Pull Chromophores [5-[[4′-(Dimethylamino)phenyl]ethynyl]-15-[(4′′-nitrophenyl)ethynyl]-10,20-diphenylporphyrinate] M(II) (M = Zn, Ni)

This work has produced experimental and theoretical evidence for the independence, on the nature of the metal, of the second order NLO response of [5-[[4′-(dimethylamino)phenyl]ethynyl]-15-[(4′′-nitrophenyl)ethynyl]-10,20-diphenylporphyrinate]M(II) NLO chromophores (M = Zn, Ni). EFISH measurements, carried out at a nonresonant 1.907 μm incident wavelength and at variable concentrations in CHCl3 or in a polar and donor solvent such as DMF or by addition of an excess of pyridine to a CHCl3 solution, have shown, together with a PGSE NMR investigation, that the different second order NLO response obtained in CHCl3 for Zn(II) and Ni(II) NLO chromophores is due to a different aggregation in CHCl3 solution. Theoretical DFT/TDDFT calculations on the NLO properties of dimeric aggregates of the NLO chromophores containing the Zn(II) center have suggested, in agreement with EFISH measurements and PGSE NMR investigation, a J aggregation which induces a doubling of the second order NLO response. The PGSE NMR investigation has also suggested a much weaker dipolar interaction for the dimerization process of the NLO chromophores containing the Ni(II) center. In this latter case the antiparallel alignment of the dipole moments of the two chromophores produces a lower second order NLO response, as experimentally observed in CHCl3 solution by increasing concentration.

Solution and Thin‐Film Aggregation Studies of Octasubstituted Dendritic Phthalocyanines

AbstractThe synthesis and solution and thin‐film characterization of eight octasubstituted dendritic phthalocyanines (Pcs) and their zinc complexes are reported. The Pc chromophore was substituted in the 2,3,9,10,16,17,23,24‐positions with three generations of benzylaryl ether dendrons with either a benzyl (3a‐3c) or 3,5‐di‐t‐butylbenzyl periphery (3d‐3f). Visible spectra in solution (CH2Cl2‐EtOH mixtures, toluene, THF, dioxane, acetone, and EtOAc) indicated a varying degree of chromophore aggregation that depended on solvent, dendrimer generation, and whether the Pc was metallated. Variable‐concentration visible spectroscopic studies were analyzed using a nonlinear least‐squares fitting procedure giving Kd values. These values further quantitated the observations that the t‐butyl‐substituted den‐drimers 3d‐3f were all less prone to aggregation in solution than the unsubstituted dendrimers 3a‐3c, with a monotonic decrease in Kd across the series 3a → 3b → 3c → 3d → 3e → 3f. Second‐generation t‐butyl‐substituted dendrimer 3f showed little to no aggregation in all solvents studied. Thin‐film studies indicated that the largest members of the two dendrimer groups, third‐generation 3c and second‐generation 3f, were largely monomeric as evidenced by split Q‐bands, similar to that seen in dilute CH2Cl2 solution when deposited via spin‐coating onto glass slides. The metallated zinc Pcs 4a‐4f all exhibited significantly less tendency toward aggregation in both solution and thin‐films than their unmetallated analogues.

Phase separation in polystyrene/poly (vinyl methyl ether) blend revealed by two-dimensional correlation resonance light scattering spectroscopy

Two-dimensional (2D) correlation resonance light scattering (RLS) spectroscopy has been successfully applied to investigate phase separation of polystyrene (PS)/poly (vinyl methyl ether) (PVME) film by using a conventional spectrofluorimeter. 2D synchronous correlation RLS spectrum indicates that the RLS peak intensity drastically increases with a rise in temperature due to aggregation of chromophores (i.e. phenyl rings) in PS particles in the course of phase separation. In addition, as concluded by 2D asynchronous correlation RLS spectrum, RLS has higher sensitivity than conventional light scattering. For RLS, the closer to the absorption band, the more sensitive it is to the aggregation during phase separation. By means of moving-window two-dimensional (MW2D) correlation spectrum based on autocorrelation calculations, the cloud point (370 K) was determined, which is in good agreement with the literature. On the other hand, time evolution of RLS intensity at various temperatures distinctly shows that phase separation of PS/PVME film involves two mechanisms, i.e. spinodal decomposition (SD) and nucleation and growth (NG). Accordingly, 2D correlation RLS proves to be a very simple and sensitive method to monitor phase separation in polymer blends and might supplement the existing characterization tools.

Ultrasonic Method for the Preparation of Organic Porphyrin Nanoparticles

We report the synthesis and optical properties of organic porphyrin nanoparticles with narrow size distribution and good dispersibility. Nanoparticles were produced by a combination of precipitation and sonication, termed the “ultrasonic method”. The resulting [tetrakis(para-chlorophenyl)porphyrin]TClPP nanoparticles were stable in solution without precipitation for at least 30 days. No self aggregation of the constituent porphyrin chromophores was observed. The TClPP nanoparticles exhibited interesting optical properties, particulalrly a large bathochromic shift in the absorption spectra.

Aggregation-induced emission: phenomenon, mechanism and applications

It is textbook knowledge that chromophore aggregation generally quenches light emission. In this feature article, we give an account on how we observed an opposite phenomenon termed aggregation-induced emission (AIE) and identified the restriction of intramolecular rotation as a main cause for the AIE effect. Based on the mechanistic understanding, we developed a series of new fluorescent and phosphorescent AIE systems with emission colours covering the entire visible spectral region and luminescence quantum yields up to unity. We explored high-tech applications of the AIE luminogens as, for example, fluorescence sensors (for explosive, ion, pH, temperature, viscosity, pressure, etc.), biological probes (for protein, DNA, RNA, sugar, phospholipid, etc.), immunoassay markers, PAGE visualization agents, polarized light emitters, monitors for layer-by-layer assembly, reporters for micelle formation, multistimuli-responsive nanomaterials, and active layers in the fabrication of organic light-emitting diodes.

Poly(methyl methacrylate) copolymers containing pendant carbazole and oxadiazole moieties for applications in single‐layer organic light emitting devices

AbstractMethyl methacrylate derived monomers functionalized with pendant carbazole and oxadiazole moieties were synthesized and could be copolymerized to form a random copolymer. The glass transition temperature of the copolymers could be predicted with a Fox equation and ranged from 140 to 191 °C. The photoluminescent characteristics of the copolymers, both in solution and in solid films, exhibited emission that was a combination of sharp and broad peaks, suggestive of monomeric and chromophore aggregation emission. These trends were also apparent in the electroluminescent response of the copolymers, where the appearance of an electromer emission was evident and was tentatively assigned to the carbazole moieties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7882–7897, 2008