Novel D − π − A dye sensitizers of polymeric metal complexes based on 8‐hydroxyquinoline and phenylethyl or fluorene units: synthesis,characterization and photovoltaic applications for dye‐sensitized solar cells

Four novel donor ? π‐bridge ? acceptor (D ? π ? A) polymeric metal complexes (P1–P4) based on 8‐hydroxyquinoline metal complexes were synthesized and tested for their performance in dye‐sensitized solar cells (DSSCs). The polymeric metal complexes dyes use alkoxy benzene or alkyl fluorene as the electron donor and C=C as π linker; the 8‐hydroxyquinoline derivative complex part was used as the electron acceptor and diaminomaleonitrile was used as ancillary ligand. The two strongly electron‐withdrawing cyano groups in the polymer structure can provide an efficient charge transport in the intramolecular between donor and acceptor parts. The thermal, photophysical, electrochemical and photovoltaic properties of these copolymers were investigated by TGA, differential scanning calorimetry, cyclic voltammetry and cureent density‐voltage curves, and the results showed that dye containing complex Zn(II) and alkoxy benzene unit benefited the generation of photocurrent and open‐circuit voltages, and a maximum power conversion efficiency of 1.91% (P2) was obtained, with an open‐circuit voltage of 0.71 V, a short‐circuit current density of 4.23 mA cm^?2, and a fill factor of 38.6% under AM1.5G irradiation. The study results also show that the four polymers exhibit good thermal stability, indicating that these polymeric metal complexes are suitable for the fabrication processes of optoelectronic devices. Copyright © 2013 John Wiley & Sons, Ltd.     

Formation and study of thin films oftert-butyl-substituted thiopyrylium dyes

The formation of thin films of symmetrical and asymmetrical thiopyrylium dyes, containingtert-butyl substituents, on glass supports was studied. The films were deposited by centrifugation of solutions of individual dyes or dye—polymer [poly(methyl methacrylate)] compositions. The dye: polymer ratios necessary for the formation of WORM recording layers based on these dyes were determined. The use of a polymeric matrix increases the film thickness and optical density but decreases its reflection power and does not allow crystallization of the dye on the support to be completely avoided. An increase in the number oftert-butyl groups in the dye molecule prevents crystallization of the recording layer in the case of symmetrical dye molecules, but does not prevent it for asymmetrical molecules. The data obtained were interpreted in terms of geometrical views on the interaction of dye molecules in thin layers. Translated fromIzestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1343–1349, July, 1998.     

Synthesis of iron-containing polymers with azo dyes in the backbones or side chains

The synthesis of cationic cyclopentadienyliron-containing polymers with pendent azobenzene chromophores was accomplished via metal-mediated nucleophilic aromatic substitution reactions. All of the desired polymers were isolated as vibrantly coloured materials and displayed excellent solubility in polar aprotic solvents. Cationic and neutral cyclopentadienyliron polymers incorporating azo dyes in the backbone were also prepared. Reactions of azo dyes with dichlorobenzene complexes allowed for the isolation of cationic cyclopentdienyliron (CpFe₊) complexes with azo dye chromophores. These complexes were then reacted with 1,1′-ferrocenedicarbonyl chloride to produce the trimetallic monomers with terminal chloro groups. These monomers contained two pendent CpFe₊ cations and a neutral iron moiety in the backbone. Nucleophilic substitution reactions of these monomers with oxygen and sulfur containing dinucleophiles gave rise to a new class of polymeric materials. The pendent CpFe₊ moieties could also be cleaved from the polymer backbones using photolysis to afford novel ferrocene based polymers. The UV-vis spectra of the organoiron monomers and polymers display similar wavelength maxima however incorporating azobenzene chromophores with electron-withdrawing substituent into the polymer chains resulted in bathochromic shifts of the λ_max values.     

Reactive Polymeric Dyes as Textile Auxiliaries

Commercial and synthetic azobenzene derivatives were used for the synthesis of hydrophilic polymeric dyes. Two strategies based respectively on the polymerization of dye methacrylic derivatives with different monomers and on the functionalization of reactive polymers were investigated. Polymers containing rather small amounts of the selected dyes were generally obtained, very likely because of the electron withdrawing effect of azo chromophores. Almost quantitative conversions were recorded in the reaction of commercial dyes with maleic anhydride/methyl vinyl ether alternating copolymers. Some of the prepared polymeric dyes were preliminarily tested as textile finishing agents.     

柱芳烃基多孔聚合物的制备及其吸附性能

将柱[5]芳烃与1,3,5-三乙炔苯(TEB)通过Sonogashira偶联反应制备了一类新型多孔有机聚合物P[5]-TEB,进而通过脱甲基反应对其进行改性得到多羟基的多孔聚合物P[5]OH-TEB,对二者的物理化学性质和吸附性能进行研究。 氮吸附测试表明,羟基的引入使P[5]OH-TEB的比表面积变大,同时引入微孔结构。 染料吸附实验表明,两聚合物对亚甲基蓝吸附过程符合Langmuir模型,P[5]OH-TEB对亚甲基蓝有更大的吸附量;吸附动力学试验表明,吸附过程更符合拟二级动力学模型,属于化学吸附过程,改性之后P[5]OH-TEB有更快的吸附速率;选择性吸附实验表明,羟基引入聚合物后聚合物对阳离子染料的吸附性能提升,对阴离子染料的吸附效果变差。     

一种含螺吡喃和肉桂酸酯双光功能基团的光致变色染料的合成与性能

合成了一种含有光致聚合肉桂酸酯基团的新型光致变色螺吡喃染料,研究其与普通螺吡喃染料在不同高分子材料中的光致变色和热退色过程(PMMA和PVCi).通过UV-Vis光谱、NMR谱和IR光谱研究了新型染料中的肉桂酸酯基团的光致聚合过程,考察了其对螺吡喃结构的光致变色显色体热稳定性的影响.     

On the photostability of some benzanthrone dye derivatives and their copolymers with methylmethacrylate

The photostability of five benzanthrone dye derivatives containing unsaturated allylic group(s) was investigated and the structure-photostability relationship was found. Their copolymers with methylmethacrylate had an intense colour, and were stable to solvents and fluorescence, due to the chemical bonding of the dye in the polymer chain. Photostability of the dyes thus included in the polymer molecule increased and their influence on the photostability of the polymers was determined.     

Photochromic and photomechanical ionene elastomer containing poly(tetrahydrofuran) segments and viologen units

Elastomeric polymer consisting of poly(oxytetramethylene) segments and viologen units (PTV) was synthesized by the reaction of dicationic living poly(tetrahydrofuran) with 4,4′-bipyridine at ?70°C. The chloride or bromide ion was introduced as the counter anion into the viologen groups of PTV by the treatment of the reaction mixture with aqueous sodium chloride or bromide, respectively. The solid film of PTV having chloride inon showed photochromism, i.e., color change by light irradiation, via photoreduction of the violegen groups. In contrast. PTV of bromide counter anion required a small amount of poly(N-vinyl-2-pyrrolidone) to undergo the photochromic reaction. The irradiation of light also affected the stress relaxation of the polymers, namely PTV showed photomechanical behavior. This phenomenon is considered to be induced by the decrease of total number of ionic charges of PTV by photo-reduction of the viologen groups followed by the change of a state of ionic clustering in the polymer matrix.     

Organoiron polynorbornenes with pendent arylazo and hetarylazo dye moieties

Organoiron polynorbornene containing arylazo or hetarylazo dye chromophores has been prepared via ring opening metathesis polymerization using Grubbs' catalyst. The obtained polymers were isolated as brightly colored materials and displayed good solubility in polar organic solvents. The colors of these polymers were affected by the nature of the incorporated azo chromophores. Thermogravimetric analysis of these materials showed that the cleavage of the cyclopentadienyliron (CpFe⁺) moieties was between 225 and 231 °C, while the degradation of the polymer backbones occurred between 400 and 450 °C. UV-vis studies in DMF showed that the organoiron polymers containing arylazo dyes exhibit wavelength maxima around 425 nm. However, the replacement of these arylazo moieties with hetarylazo dyes displayed substantial bathochromic shifts in the λ_max values (≈ 511 nm).     

Synthesis and characterization of colored EUDRAGIT® as enteric coating material

The synthesis of novel polymeric dyes by directly attaching toluidine blue O and MPPD via EDC and CDI coupling is described for polymers with enteric properties [poly(methacrylic acid‐co‐ethyl acrylate)]. The polymeric dyes are analyzed by SEC and UV/Vis measurements as well as investigated regarding their dissolution and permeation characteristics. Almost no changes between the modified and nonmodified polymer could be observed by conventional drug studies and a self‐established method for dissolution rates. Also no influence on the film formation properties was observed by SEM measurements. In vitro toxicity studies showed no increase of toxicity compared to the non modified polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2386–2393     

Temperature‐Controlled Switchable Photochromism in Solid Materials

A novel strategy to achieve thermally switchable photochromism in solid materials is reported, which relies on the preparation of polymeric core–shell capsules containing solutions of photochromic dyes in acidic phase‐change materials. Upon changing the phase (solid or liquid) of the encapsulated medium, one of the two photochromic states of the system is selectively stabilized on demand, allowing for reversible interconversion between direct and reverse photochromism when thermally scanning through the melting temperature of the phase‐change material. This strategy, which does not require the addition of external agents or chemical modification of the dyes, proved to be general for different spiropyran photochromes and to be applicable to the fabrication of a variety of functional materials by simply embedding the capsules obtained into a solid matrix of choice.     

Photoresponsive liquid crystalline and amorphous polymers

Isomerization processes of azobenzene dyes dissolved in a glassy polymeric matrix or attached in glassy amorphous or liquid crystalline polymers to the backbone as side groups are induced by light. The isomerization process, in turn, causes the dye to reorient provided that polarized light is used: the long axis of the dye is oriented perpendicular to the polarization direction in the stationary case. Such a reorientation gives rise to strong modifications of the optical properties. This contribution is concerned with the analysis of the correlation between the nature of the azobenzene dyes, the isomerization, reorientation and modulations discussed above and with possible applications in the optical holographic storage. Considered are, in particular, dye/matrix combinations giving rise to nonlinear holographic responses, two photon holography, transient holographic modes applicable for holographic displays and the optical switching of other than optical properties.     

共聚型环氧树脂基高分子染料的制备和表征

合成了环氧基先驱聚合物,采用后重氮偶合反应经一步法在聚合物中同时引入两种不同颜色的偶氮生色团.通过调配重氮盐的比例制备了一系列具有不同颜色及玻璃化转变温度的高分子染料.利用氢核磁共振谱图(1H-NMR)计算了聚合物上两种偶氮生色团的官能化度,采用示差扫描量热仪(DSC)测量了不同高分子染料的玻璃化转变温度(Tg)和分解温度(Td),用分光光度仪对这些聚合物的颜色进行了表征,并在国际照明委员会(CIE)颁布的CIE 1931 Yxy色度图上标出了相应的位置.结果表明:这些聚合物具有良好的溶解性、成膜性强、附着力强,可以应用于彩色滤光片等.     

高分子染料的进展

高分子染料是一类本身固有颜色的高分子化合物，它兼有染料和高聚物的双重性质。因此既可作为色料也可作为高聚物而应用于许多领域。本文较详细阐述了聚合染料的种类，合成方法及应用情况。     

Release of a dye from hydrogen-bonded and electrostatically assembled polymer films triggered by adsorption of a polyelectrolyte

The absorption of dyes within hydrogen-bonded and electrostatically assembled multilayers and subsequent release of the dyes from the films were studied in situ using FTIR-ATR. Multilayers were composed of poly(methacrylic acid), PMAA, and poly(ethylene oxide), PEO (hydrogen-bonded multilayers), or of PMAA and 22% quarternized copolymer of N-ethyl-4-vinylpyridium bromide and 4-vinylpyridine, Q22 (electrostatically stabilized multilayers). After multilayer deposition, the solution pH was changed to produce excess charge within the films. Dyes with charge opposite to the excess charge of the film (Rhodamine 6G for hydrogen-bonded films or Bromophenol Blue for electrostatically assembled multilayers) were then allowed to absorb within multilayers. In both systems, the dyes were uniformly included within the films. The top layers largely affected the loading capacity of the multilayers, suggesting weaker binding of the dyes with the top layers. Dye release into a 0.01 M phosphate buffer was significantly smaller as compared to release in the presence of 0.05-0.5 mg/mL solutions of adsorbing polymers whose charge was the same as the excess charge within the films. We found that with the PMAA/PEO films, dye release did not depend on the concentration of polymer in solution, but was largely controlled by the amount of charge accumulated within the adsorbing polymer layer on the top of the film. For electrostatically stabilized PMAA/Q22 systems, dye release increased with increasing concentration of Q22 in solution, suggesting a significant contribution of the competition of solution species in the release mechanism. Our findings contribute to the understanding of interactions of small molecules with polymer multilayers and might have ramifications for novel applications of multilayer films as new materials for the controlled delivery of chemicals.     

Quantitative treatment of the dye partition method of analysis of surfactants and of ionic groups in high polymers

A quantitative treatment of the extraction of ionic dyes from aqueous solutions into organic solvents of low dielectric constant by surfactants or polymers with ionic groups having a charge opposite to that of the dye ion, is presented. The assumption is made that the extracted species are ion-paired in the organic phase. Based on this, a graphical extrapolation method is suggested for the quantitative estimation of ionic groups in polymers. Theoretically, the method should yield quantitative results irrespective of polymer chain length and character. This method of analysis does not require any calibration data.     

A study on optical limiting properties of Eosin-Y and Eriochrome Black-T dye-doped poly (vinyl alcohol) composite film

A poly (vinyl alcohol) PVA/Eriochrome Black-T (EBT) dye, and PVA/Eosin-Y (EY) dye composite film was prepared using a solution casting process. The dye-doped composite polymer films were characterized by UV–vis spectroscopy. An optical band gap (E_g) of pure PVA reduced from 4.22?eV to 2.80?eV for PVA/EBT film and 2.14?eV for PVA/EY film respectively. This result indicates the occurrence of inter-molecular hydrogen bonding between the –OH functional group in PVA chains and sulfonate (EBT) and carboxyl group (EY) in dye molecules, respectively. Moreover, the experimental result of PVA/EBT and PVA/EY composite film showed the excellent properties of a large scale cut-off filter in the ultraviolet and visible range region.     

Interactions between poly(2-ethylacrylic acid) and lipid bilayer membranes: effects of cholesterol and grafted poly(ethylene glycol)

The exchange of the protonatable polymer, poly(2-ethylacrylic acid) (PEAA), has been studied with vesicle membranes containing cholesterol from 0 to 60 mol% or PEG2000-lipid (5 mol%). The release of an entrapped dye from 100 nm extruded liposomes was used as an assay for membrane perturbation by the polymer as a function of pH. The inclusion of cholesterol was found to reduce the pH at which the polymer caused release of the dye from the lipid vesicles, and the degree of polymer protonation (i.e., degree of hydrophobicity) correlated well with the increase in elastic expansion modulus of the vesicle bilayer. The results are discussed in terms of a balance between polymer solubility and membrane expansion. With respect to the PEG barrier, the presence of 5 mol% PEG2000, which represents full surface coverage, did not prevent PEAA from inducing contents release, demonstrating that highly hydrated polymeric layers are not effective barriers for other water soluble polymers, and may point to some association between the two polymers.     

Selective recognition and discrimination of water‐soluble azo dyes by a seven‐channel molecularly imprinted polymer sensor array

A seven‐channel molecularly imprinted polymer sensor array was prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, UV‐Vis spectroscopy, and nitrogen physisorption studies. The results revealed that the imprinted polymers have distinct‐binding affinities from those of structurally similar azo dyes. Analysis of the UV‐Vis spectral response patterns of the seven dye analytes against the imprinted polymer array suggested that the different selectivity patterns of the array were closely connected to the imprinting process. To evaluate the effectiveness of the array format, the binding of a series of analytes was individually measured for each of the seven polymers, made with different templates (including one control polymer synthesized without the use of a template). The response patterns of the array to the selected azo dyes were processed by canonical discriminant analysis. The results showed that the molecularly imprinted array was able to discriminate each analyte with 100% accuracy. Moreover, the azo dyes in two real samples, spiked chrysoidin in smoked bean curd extract and Fanta lime soda (containing tartrazine), were successfully classified by the array.     

Synthesis of polymeric 1‐iminopyridinium ylides as photoreactive polymers

Two synthetic routes to polymeric 1‐imino pyridinium ylides as new photoreactive polymeric architectures were investigated. In the first approach, polymerization of newly synthesized 1‐imino pyridinium ylide containing monomers yielding their polymeric analogues was achieved by free radical polymerization. Alternatively, reactive precursor polymers were synthesized and converted into the respective 1‐imino pyridinium ylide polymers by polymer analogous reactions on reactive precursor polymers. Quantitative conversion of the reactive groups was achieved with pentafluorophenyl ester containing polymers and newly synthesized photoreactive amines as well as by the reaction of poly(4‐vinylbenzoyl azide) with a photoreactive alcohol. The polymers obtained by both routes were examined regarding their photoreaction products and kinetics in solution as well as in thin polymer films. Contact angle measurements of water on the polymer films before and after irradiation showed dramatic changes in the hydrophilicity of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 832–844, 2010