Dye Monomers Research Articles

A General Strategy to Enhance the Performance of Dye-Sensitized Solar Cells by Incorporating a Light-Harvesting Dye with a Hydrophobic Polydiacetylene Electrolyte-Blocking Layer.

A unique strategy to suppress charge recombination effectively and enhance light harvesting in dye-sensitized solar cells (DSSCs) is demonstrated by the design of a new dipolar organic dye functionalized with a diacetylene unit, which is capable of undergoing a photoinduced crosslinking reaction to generate a hydrophobic polydiacetylene layer. The polydiacetylene layer serves as an electrolyte-blocking layer that effectively blocks the approach of the oxidized redox mediator and suppresses the dark current, and also plays a role in light harvesting owing to efficient energy transfer to the dipolar dyes. A 15 % efficiency improvement was achieved on going from the monomer dye (JSC =13.5 mA cm-2 , Voc =0.728 V, fill factor=0.73, η=7.17 %) to the crosslinked dye (JSC =14.9 mA cm-2 , Voc =0.750 V, fill factor=0.74, η=8.27 %) under AM 1.5 conditions.

Plasmon–Exciton Coupling between Metallic Nanoparticles and Dye Monomers

We investigate electromagnetic coupling between localized surface plasmons and excitons in a Ag nanoparticle (NP) and monomer dye conjugate. Strong coupling is observed as Rabi splitting in the optical scattering response of the conjugate. We measure the strength of coupling as a function of NP–dye separation distance using bifunctional molecules that link the dye and NP with nanoscale control. Coupling strength follows a single-exponential decay with a decay length of 13.7 ± 5 nm, indicating that the conjugates can be used as a plasmon ruler. In addition, we find that at separation distances below 2 nm the coupling strength is strongly decreased by quantum effects such as electron tunneling which interfere with plasmon–exciton hybridization. Using single NP spectroscopy to investigate conjugate coupling energy, we are able to tune separation distance to achieve coupling energies as high as 600 meV, among the highest energies reported for Ag NPs.

Spectral-fluorescent study of the interaction of the polymethine dye probe Cyan 2 with chondroitin-4-sulfate

The noncovalent interaction of the polymethine dye probe 3,3′,9-trimethylthiacarbocyanine iodide (Cyan 2) with chondroitin-4-sulfate (C4S) in buffer solutions with different pH and in water in the absence of buffers has been studied by spectral-fluorescent methods. It has been shown that in all media studied, at relatively high concentrations, the dye is bound to C4S mainly as a monomer, which is accompanied by a steep rise of fluorescence (the intermediate formation of dye aggregates on the biopolymer is also observed). From the dependence of the fluorescence quantum yield on the concentration of C4S, the parameters of binding of the dye monomer to C4S were obtained: the effective binding constant K, the number of the monomeric C4S units n per one dye monomer bound to C4S, and the fluorescence quantum yield of the bound dye monomer Φfb. The dependence of Φfb (and K) on рН of the medium is not monotonic: it has a minimum in the region of neutral pH and a growth in the regions of acid and basic pH. This can be explained by changing the charge of a C4S macromolecule as a function of pH and related conformational alterations in the biopolymer, which can affect the rigidity of a dye molecule and the energy of its interaction with the biopolymer.

Formation of trans-2-[4-(Dimethylamino)Styryl]-3-Ethyl-1,3-Benzothiazolium Perchlorate Dimers in the Presence of Sodium Polystyrene Sulfonate

The spectral properties of a novel thioflavin T derivative, trans-2-[4-(dimethylamino)styryl]-3-ethyl-1,3-benzothiazolium perchlorate (DMASEBT), were studied in aqueous solutions in the presence of sodium polystyrene sulfonate (SPS). It was shown that SPS either could interact with dye monomers or initiate the formation of non-fluorescent dye dimers depending on the concentration ratio of dye and polyelectrolyte. DMASEBT dimer formation in the presence of SPS produced a hypsochromic shift by 40 nm in the absorption spectrum and quenched fluorescence. A bathochromic shift of the absorption spectrum and an increase of the fluorescence intensity by an order of magnitude were observed if DMASEBT monomers interacted with SPS. Quantum-chemical analysis found that sandwich dimers (H-aggregates) were most stable. A comparison of DMASEBT spectra in the presence of SPS and amyloid fibrils showed that DMASEBT molecules were incorporated into amyloid fibrils as monomers. The spectral changes associated with this incorporation could not be explained by the formation of dye aggregates.

Aggregation behavior of novel heptamethine cyanine dyes upon their binding to native and fibrillar lysozyme.

Two newly synthesized symmetrical heptamethine cyanine dyes, AK7-5 and AK7-6, absorbing in the region of low autofluorescence of biological samples, have been tested for their ability to detect proteins aggregated into amyloid fibrils. In aqueous solution these probes possess three absorption bands corresponding to the monomer, dimer and H-aggregate species. The association of the dye with fibrillar lysozyme was followed by the enhancement of the monomer band and the reduction of the H-band. The absorption spectra measured at various fibril concentrations were analyzed in terms of the model allowing for the shift of equilibria between various dye species due to the binding of monomers and dimers of AK7-5 and AK7-6 to amyloid fibrils. The association constants and stoichiometries of the dye-fibril complexation have been evaluated. In contrast to fibrillar lysozyme, the native protein brought about strong J-aggregate formation accompanied by a marked drop in the absorbance of the dye monomer species. Quantum chemical calculations and simple docking studies showed that AK7-5 and AK7-6 monomers can bind to the grooves, running parallel to the fibril axis. Due to their ability to distinguish between the native and fibrillar protein states, the novel cyanines are recommended as complementary to existing amyloid markers.

Aerogels containing 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin with controlled state of aggregation

Aerogels made of chitosan and chondroitin sulfate, and containing 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin have been synthesized. The aerogels presented a microstructure made of microfibers and microsheets, with porosity higher than 99%. The dispersion and state of aggregation of the dye in the solids have been controlled with the aid of aromatic polyelectrolytes able to produce aromatic-aromatic interactions. Thus, non-homogenous dispersions of the dye as J-aggregates and formation of microcrystals on the microsheet surface were observed in the absence of the aromatic polymers; on the contrary, well dispersed H-aggregates of the dye were observed in the presence of poly(decylviologen), and well dispersed complexed monomeric dye molecules were found in the presence of a polyketone derivatized with hystamine, thus presenting imidazolium pendant groups. The same state of aggregation has been observed in solution for the respective complexes, highlighting the potential of aromatic-aromatic interactions to achieve a control of the state of aggregation of dyes in solution and further transfer to the solid state keeping their photophysical properties, and furnishing means for a good dispersion of the dyes in solid materials.

Bichromatic coherent random lasing from dye-doped polymer stabilized blue phase liquid crystals controlled by pump light polarization**Project supported by the National Natural Science Foundation of China (Grant Nos. 11474021 and 51333001), the Key Program for International S&T Cooperation Projects of China (Grant No. 2013DFB50340), the Issues of Priority Development Areas of the Research Fund for the Doctoral Program of Higher

In this paper, we investigate the bichromatic coherent random lasing actions from the dye-doped polymer stabilized blue phase liquid crystals. Two groups of lasing peaks, of which the full widith at half maximum is about 0.3 nm, are clearly observed. The shorter- and longer-wavelength modes are associated with the excitation of the single laser dye (DCM) monomers and dimers respectively. The experimental results show that the competition between the two groups of the lasing peaks can be controlled by varying the polarization of the pump light. When the polarization of the pump light is rotated from 0° to 90°, the intensity of the shorter-wavelength lasing peak group reduces while the intensity of the longer-wavelength lasing peak group increases. In addition, a red shift of the longer-wavelength modes is also observed and the physical mechanisms behind the red-shift phenomenon are discussed.

Non-covalent incorporation of some substituted metal phthalocyanines into different gel networks and the effects on the gel properties

The use of metallo-phthalocyanines (MPcs) in many technological applications requires the development of specific methods for flexible thin film fabrication. An interesting and simple strategy is the physical encapsulation of MPcs within viscoelastic gel scaffolds. However, non-covalent incorporation of large external molecules into gel networks is a challenge because the balance between dissolution and crystallization in metastable gel phases is likely to be altered changing the properties and/or stability of the material and, therefore, threatening its functionality. In this work, we report preliminary results regarding non-covalent inclusion of MPcs into different gel networks and the effects on their thermal, morphological and mechanical properties. In general, slight variations on the [Formula: see text]were observed for most combinations prepared at well-defined concentrations in the presence of suitable MPcs, except for the organogel made of peracetylated [Formula: see text]-cyclodextrin and the hydrogel made of a bile acid-based gelator. These gels experienced a remarkable enhancement of the [Formula: see text] of ca. 20°C with respect to the pristine gels. Moreover, preservation of monomeric dye species and reduced photodegradation was also observed in some hybrid gels. Relative correlations between thermal stability, morphological features and mechanical properties were also drawn during the study. Maintenance of the catalytic activity of a CuPc immobilized in a supramolecular gel network was also demonstrated by the aerobic oxidation of benzhydrol to benzophenone at room temperature.

Synthesis and fluorescence properties of a waterborne polyurethane–acrylic hybrid polymeric dye

A waterborne polyurethane–acrylic hybrid polymeric dye was prepared depending on soap-free emulsion polymerization method. The resulting polymeric dye composed of methyl methacrylate (MMA) monomer which was polymerized into polymethyl methacrylate (PMMA) as cores and waterborne polyurethane-based dye was synthesized by anchoring dye monomers (6-amino-2-cyclohexyl-benz[de]isoquinone-1,3-dione) to polyurethane chains as shells. The average particle sizes of the hybrid polymeric dye emulsions were found to be increased with the increase in MMA contents for MMA monomers. Compared with dye monomers, the absorption intensities and fluorescence intensities of the hybrid polymeric dye were enhanced with the increase of particle sizes. This study revealed that enhanced fluorescence intensity of the hybrid polymeric dye was mainly attributed to the hindered formation of exciplexes among dye monomers and an augmented light absorption area. It was found that the fluorescence intensity of the hybrid polymeric dye was increased with increasing temperature and the trend first increased and then decreased with increase in concentration. Furthermore, the fluorescence of the hybrid polymeric dye emulsions was found to be very stable and not sensitive to the fluorescence quencher.

Optoelectronic and Photovoltaic Performances of Pyridine Based Monomer and Polymer Capped ZnO Dye-Sensitized Solar Cells.

The present research work describes the comparative analysis and performance characteristics of 4-pyridine based monomer and polymer capped ZnO dye-sensitized solar cells. The N, N-dimethyl-N4-((pyridine-4yl)methylene) propaneamine (4,monomer) and polyamine-4-pyridyl Schiff base (5, polymer) dyes were synthesized through one step condensation reaction between 4-pyridinecarboxaldehyde 1 and N, N-dimethylpropylamine 2/polyamine 3. Products obtained N, N-dimethyl-N4-((pyridine-4yl)methylene)propaneamine (4) and polyamine-4-pyridyl Schiff base (5) were purified and characterized using 1H, 13C NMR, mass, IR and CHN spectroscopy. Both the dyes 4 and 5 were further coated over ZnO nanoparticles and characterized using SEM, DLS and XRD analysis. Absorption profile and emission profile was monitored using fluorescence and UV-Vis absorption spectroscopy. A thick layer of these inbuilt dye linked ZnO nanoparticles of dyes (4) and (5) was pasted on one of the conductive side of ITO glass followed with a liquid electrolyte and counter electrode of the same conductive glass. Polyamine-4-pyridyl Schiff base polymer (5) decorated dye sensitized solar cell has shown better exciting photovoltaic properties in the form of short circuit current density (J(sc) = 6.3 mA/cm2), open circuit photo voltage (V(oc) = 0.7 V), fill factor (FF = 0.736) than monomer decorated dye sensitized solar cell. Polymer dye (5) based ZnO solar cell has shown a maximum solar power to electrical conversion efficiency of 3.25%, which is enhanced by 2.16% in case of monomer dye based ZnO solar cell under AM 1.5 sun illuminations.

Novel synthetic approach to near-infrared heptamethine cyanine dyes and spectroscopic characterization in presence of biological molecules

Abstract Two near-infrared symmetric heptamethine cyanine dyes, containing integrated chlorosubstituted cyclohexenyl ring were obtained via a novel synthetic approach, using mild conditions at room temperature. UV–vis and fluorescence properties of the dyes were evaluated in organic solutions varying solvent polarity. Further spectral studies illustrating their application as potential labels for biological molecules, were reported in the presence of deoxyribonucleic acid (DNA), bovine serum albumin (BSA), and phospholipids (PC). The dyes undergo H-type intramolecular complexation between the two cyanine subunits when free in buffer. Absorption studies show that binding of cyanines to DNA, BSA and lipid membranes leads to the red shift in the H-aggregates peak with appearance of monomeric and dimeric dye species pointing to the disaggregation of the dyes under study in the presence of biological molecules. The fact that the decrease of liposome-induced cyanine aggregation was more pronounced in the zwitterionic phosphatidylcholine bilayer, suggests that the disruption of highly organized molecular arrangements are most likely electrostatically-controlled.

Influence of the Near Molecular Vicinity on the Temperature Regulated Fluorescence Response of Poly(N-vinylcaprolactam).

A series of new fluorescent dye bearing monomers, including glycomonomers, based on maleamide and maleic esteramide was synthesized. The dye monomers were incorporated by radical copolymerization into thermo-responsive poly(N‑vinyl-caprolactam) that displays a lower critical solution temperature (LCST) in aqueous solution. The effects of the local molecular environment on the polymers’ luminescence, in particular on the fluorescence intensity and the extent of solvatochromism, were investigated below as well as above the phase transition. By attaching substituents of varying size and polarity in the close vicinity of the fluorophore, and by varying the spacer groups connecting the dyes to the polymer backbone, we explored the underlying structure–property relationships, in order to establish rules for successful sensor designs, e.g., for molecular thermometers. Most importantly, spacer groups of sufficient length separating the fluorophore from the polymer backbone proved to be crucial for obtaining pronounced temperature regulated fluorescence responses.

Zeolite matrix assisted decomposition of singlet oxygen sensitizers during photooxidation

Abstract Thiazine dyes such as thionine, methylene blue and methylene green were exchanged within monovalent cation exchanged Y zeolites. Depending on the water content the dye molecules exist as either monomer (‘dry’) or dimer (‘wet’). The monomeric dye is effective in producing singlet oxygen by energy transfer process inside the zeolite cavity. In polar zeolites like LiY, NaY energy transfer predominates whereas in basic zeolites like CsY electron transfer overtakes the energy transfer leading to the photo-destruction of the dye. While on short time of irradiation, energy transfer to oxygen led to selectivity in the product distribution, but on prolonged irradiation, destruction of the dye through electron transfer was the main outcome.

Selenorhodamine Dye-Sensitized Solar Cells: Influence of Structure and Surface-Anchoring Mode on Aggregation, Persistence, and Photoelectrochemical Performance.

A library of six selenorhodamine dyes (4-Se-9-Se) were synthesized, characterized, and evaluated as photosensitizers of TiO2 in dye-sensitized solar cells (DSSCs). The dyes were constructed around either a bis(julolidyl)- or bis(half-julolidyl)-modified selenoxanthylium core functionalized at the 9-position with a thienyl group bearing a carboxylic, hydroxamic, or phosphonic acid for attachment to TiO2. Absorption bands of solvated dyes 4-Se-9-Se were red-shifted relative to the dimethylamino analogues. The dyes adsorbed to TiO2 as mixtures of monomeric and H-aggregated dyes, which exhibited broadened absorption spectra and increased light-harvesting efficiencies relative to the solvated monomeric dyes. Carboxylic acid-bearing dyes 4-Se and 7-Se initially exhibited the highest incident photon-to-current efficiencies (IPCEs) of 65-80% under monochromatic illumination, but the dyes desorbed rapidly from TiO2 into solutions of HCl (0.1 M) in a CH3CN:H2O mixed solvent (120:1 v:v). The hydroxamic acid- and phosphonic acid-bearing dyes 5-Se, 6-Se, 8-Se, and 9-Se exhibited lower IPCEs (49-65%) immediately after preparation of DSSCs; however, the dyes were vastly more inert on TiO2, and IPCEs decreased only minimally with successive measurements under constant illumination. Power-conversion efficiencies (PCEs) of the selenorhodamine-derived DSSCs were less than 1%, probably due to inefficient regeneration of the dyes following electron injection. For a given anchoring group, the bis(half-julolidyl) dyes exhibited higher open-circuit photovoltages and PCEs than the corresponding bis(julolidyl) dyes. The hydroxamic acid- and phosphonic acid-bearing dyes are intriguing photosensitizers of TiO2 in light of their aggregation-induced spectral broadening, high monochromatic IPCEs, and relative inertness to desorption into acidic media.

The thin films of pyronin dyes doped with poly(vinyl sulphate) on glass substrate: Preparation and characterization

The thin films of pyronin B (PyB) and pyronin Y (PyY) mixed with poly(vinyl sulphate) (PVS) on glass substrate from aqueous solution were fabricated using a simple spin-coating film technique. The photophysical properties of the thin films were examined by UV–Vis, steady-state fluorescence and time-resolved fluorescence spectroscopy techniques. The dye thin films on the glass substrate were prepared at various [PVS]/[dye] ratios. The interactions of pyronin dyes with PVS caused the formation of monomeric and H-aggregate thin films of the dyes. H-aggregates of pyronin dyes in the thin film quenched their fluorescence intensities while the monomeric dye films have strong fluorescence. Moreover, the presence of H-aggregates in the thin film also decreased the fluorescence lifetimes of dyes. The morphological variations in the thin films depending on the dye concentration were investigated by AFM. The morphological analysis of the thin films revealed that the thin films including H-aggregates were predominant in fibril-like structures while the monomeric thin films displayed the same morphologies compared to that observed in pristine PVS film. When the spectroscopic and morphological results were evaluated, it was concluded that H-aggregates of pyronin dyes were formed due to the adsorption of the dyes on PVS backbone.

Efficient solid-state dye sensitized solar cells: The influence of dye molecular structures for the in-situ photoelectrochemically polymerized PEDOT as hole transporting material

Solid-state dye sensitized solar cells (sDSCs) with organic small molecule hole transporting materials (HTMs) have limited efficiencies due to the incomplete pore filling of the HTMs in the thick mesoporous electrodes and the low hole conductivity of HTMs. Hereby, highly efficient sDSCs with power conversion efficiency of 7.11% and record photocurrent of 13.4mAcm−2 are reported, prepared by effectively incorporating in-situ photoelectrochemically polymerized PEDOT as HTM in combination with a multifunctional organic, metal-free dye. In order to fundamentally understand how the dye molecules affect the photoelectrochemical polymerization (PEP), the properties of the generated PEDOT and the photovoltaic performance, sDSCs based on a series of dyes are systematically investigated. Detailed comparative studies reveal that the difference between the dye redox potential and monomer onset oxidation potential plays a crucial role in the PEP kinetics and the doping density of PEDOT HTM. The structure of the dyes, functioning as an electron blocking layer, affects the charge recombination at the TiO2/dye/PEDOT interface. The analysis shows that a donor-π-acceptor dye with well-tuned energy levels and bulky structure results in an in-situ electrochemically doped PEDOT HTM with a high hole conductivity (2.0Scm−1) in sDSCs, leading to efficient dye regeneration and photocharge collection. It is hoped that this work will further encourage research on the future design of new dye molecules for an efficient PEP in order to further enhance the photovoltaic performance of solid-state dye sensitized solar cells.

Dye Encapsulation in Polynorbornene Micelles.

The encapsulation efficiency of high-Tg polynorbornene micelles was probed with a hydrophobic dye 2,6-diiodoboron-dipyrromethene (BODIPY). Changes in the visible absorption spectra of aggregated versus monomeric dye molecules provided a probe for assessing encapsulation. Polynorbornene micelles are found to be capable of loading up to one BODIPY dye per ten polymers. As the hydrophilic block size increased in the polymeric amphiphiles, more of the dye was incorporated within the micelles. This result is consistent with the dye associating with the polymer backbone in the shell of the micelles. The encapsulation rate varied significantly with temperature, and a slight dependence on micellar morphology was also noted. Additionally, we report a 740 μs triplet lifetime for the encapsulated BODIPY dye. The lifetime is the longest ever recorded for a BODIPY triplet excited state at room temperature and is attributed to hindered triplet-triplet annihilation in the high-viscosity micellar shell.

Surfactant induced aggregation behavior of Merocyanine-540 adsorbed on polymer coated positively charged gold nanoparticles

Surfactant induced aggregation behavior of Merocyanine 540 adsorbed on polymer (PDD) coated gold nanoparticles (AuNP) is reported. The absorption band of the dye shifts to higher energy in the presence of free polymer and polymer coated AuNP implying aggregation. Addition of a negatively charged surfactant (SDS) induces multiple bands in the extinction spectrum of the dye adsorbed on nanoparticle surface. The highest (460nm) and lowest (564nm) energy bands of the dye become prominent at 10 and >50μM SDS concentrations respectively (dye: 10μM; AuNP: 100–200pM). Based on earlier results the high energy band is likely to originate from dye aggregates and the low energy band is likely to originate from dye monomers. This is attributed to the interplay between polymer–surfactant and polymer–dye interactions at the AuNP surface. The extinction spectra of dye adsorbed at AuNP surface remain unaffected in the presence of a positively charged (CTAB) or a neutral surfactant (Tx-100), at low surfactant concentrations. However at higher surfactant concentrations (>60μM) dye aggregation takes place which is attributed to dye–surfactant interactions. The fluorescence intensity of the dye quenched significantly but its lifetime increased in the presence of polymer coated AuNP. This is attributed to aggregation and reduction in the photoisomerization rate of the dye adsorbed on AuNP surface.

On the origin of oscillations in two-dimensional spectra of excitonically-coupled molecular systems

We investigate an artificial molecular dimer made of two dipole coupled cyanine dye monomers in which a strong coherent coupling between electronic and vibrational degrees of freedom arises. Clear signatures of this coupling are reflected in an oscillatory time evolution of the off-diagonal vibronic cross peaks in the two-dimensional optical photon echo spectrum. We find a strong coherence component damped by fast electronic dephasing ( fs) accompanied by a much weaker component which decays on the longer time scales (ps) associated to vibrational dephasing. We find that vibronic coupling does not cause longer dephasing times of the dominant photo echo component but additional weak but long-lived components emerge.

Molecular Reorganization Energy as a Key Determinant of J-Band Formation in J-Aggregates of Polymethine Dyes.

This work demonstrates the feasibility of the theory of extended multiphonon electron transitions for the description of optical spectra of polymethine dyes and J-aggregates using quantum chemistry. The formation of a strong absorption band in dye monomers and a J-band in their aggregates is uniformly explained from the electron-nuclear resonance condition. The redistribution of optical band intensities among cyanine dyes with the solvent is also explained. The dependence of the possibility of J-band formation in aggregates on the dye structure is successfully predicted. The results presented provide an insight for rational molecular design and application of polymethine dyes.