Photo-induced morphology transition of a multifunctional photochromic bisthienylethene molecule with switchable aggregation-induced emission

A novel multifunctional molecule BTE-CNPH was designed and synthesized by connecting 2-(3′,5′-bis(trifluoromethyl)-biphenyl-4-yl)-2-cyanovinyl group to both side of the bisthienylethene(BTE), which exhibited excellent aggregation-induced emission(AIE) and bistable photochromism. High-contrast(60) reversible fluorescence switching was achieved in the 1 D nanowires, solid of BTE-CNPH and also in a polymethyl methacrylate(PMMA) film loaded with 1% BTE-CNPH under the alternative irradiation by 365 nm and visible light. Interestingly, the nanowire-like assembly morphology of BTE-CNPH in aqueous tetrahydrofuran(THF) solution of specific concentration was observed to translate into amorphous pieces gradually upon prolonged irradiation by the 365 nm, accompanying with photo-tunable AIE emission.     

Preparation and Visible-light Photochromism of Phosphomolybdic Acid/Polyvinylpyrrolidone Hybrid Film

The visible-light photochromic hybrid film was constructed by entrapping phosphomolybdic acid（PMoA） into polyvinylpyrrolidone（PVPd） networks. The microstructure, photochromic properties and mechanism were inves- tigated with transmission electron microscopy（TEM）, atomic force microscopy（AFM）, Fourier transform infrared （FTIR） spectroscopy, ultraviolet-visible（UV-Vis） spectra and X-ray photoelectron spectroscopy（XPS）. The results in- dicate that the Keggin geometry of PMoA and the basic structure of PVPd are not destroyed during the composite process. Irradiated with visible light, the transparent PMoA/PVPd film changes color from colorless to blue and ex- hibits reversible photochromism in the presence of oxygen. According to the XPS analysis, the charge-transfer bridge of N-H-O has been built between PMoA and PVPd matrix via non-covalent bonding, and the appearance of Mo5＋ species indicates that the photo-reduction process is in accordance with the proton transfer mechanism.     

Crystal Structure and Crystalline State Multiphotochromism Properties of a Fused Diarylethene Dimer

The crystal structure of fused photochromic diarylethene dimer, 1,4-bis-[4-(4-{2-(5-phenyl)-2-methyl-thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-cyclopent-1-enyl}-5-methyl-thiophen-2-yl) buta-1,3-diyne(1 oo, C46 H23 F12 S4) was determined by single-crystal X-ray diffraction analysis. This crystal belongs to the triclinic system, space group P1 with a = 7.546(3), b = 8.869(3), c = 16.196(5), α = 98.000(4)°, β = 100.803(4)°, γ = 98.449(4)°, Z = 2, V = 1037.6(6) ?~3, Dc = 1.496 mg/m~3, μ = 0.317, F(000) = 474, the final R = 0.0428 and wR = 0.1199 for 4115 observed reflections(I 2σ(I)). Further study demonstrated this compound underwent reversible photochromism with color-switching between colorlessness and green in crystalline state. Upon 365 nm irradiation, the diarylethene shows one step photochromism to form isomer 1 oc. When irradiated with 312 nm, the stepwise photocyclization reactions occurred in diarylethene dimer through the line of 1 oo to 1 oc to 1 cc.     

Investigation on Viscoelasticity of Waterborne Polyurethane with Azobenzene-containing Pendant Groups under Ultraviolet and Visible-light Irradiation

In this study, a novel waterborne polyurethane(WPU) with azobenzene-containing(azo-containing) pendant groups was synthesized by isophorone diisocyanate, long-chain diol of polycaprolactone, 2-ethyl-2-methyl-butanoic acid(2,2-dimethylolpropionic acid), 10-(4-(phenyldiazenyl)phenoxy)decyl-3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate, and N,N-diethyl-ethanamine(triethylamine). Moreover, the influence of ultraviolet and visible(UV-Vis) light irradiation on the viscoelasticity of azo-containing WPU film in terms of the reversible trans-cis photoisomerization of azo-containing pendant groups was investigated by UV-Vis light spectroscopy,atomic force microscopy, and dynamic thermomechanical analysis. The results revealed that the adhesion of azo-containing WPU with single crystal silicon atomic force microscope probe was about 13 n N when irradiated by 450 nm Vis light for 60 s at 25 °C. Subsequently,the adhesion increased to 82 n N after irradiation with 365 nm UV light for 60 s at 25 °C. In addition, the azo-containing WPU presented a photo-induced reversible transition of tensile modulus and tanδ in the range from about 2 MPa to 22 MPa and 6000 to 0.35 with UV-Vis light cyclic irradiation for 120 s at 25 °C, respectively.     

具有多个光致变色单元的二芳基乙烯分子光密度的增加

3,4-Diaryl-2,5-dihydropyrrole with multiphotochromophore units la was synthesized and its photochromic properties were investigated. It showed that all photochromophore units underwent reversible ring-opening （1a） and ring-closing （1b） photoisomerization reactions in both solution and polymer film with UV/Vis light irradiation, and photochromic properties of la were similar to those of photochromic diarylethene with monophotochromophore 2a. It was found that the optical density of lb was increased linearly with increase of the photochromophore units by comparison with that of 2b in the same condition. It was also found that no significant changes in absorption band and response time between diarylethenes with multiphotochromophores and monophotochromophore were detected in the same condition.     

Nafion-lnduced Metal-Metal Interactions in a Platinum（Ⅱ） Terpyridyl Acetylide Complex： a Luminescent Sensor for Detection of Volatile Organic Compounds

The platinum(Ⅱ) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2‘ : 6‘2“-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nation membranes. At high loading the dry membranes exhibit intense photoluminescence with λmax at 707 nm from the ^3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nation-supported complex as an interesting sensor candidate for polar VOC.     

In situ Observation of the Photochromism in the Langmuir Monolayer of a Non—typical Amphiphilic Spiropyran Derivative at the Air／Water Interface

In situ photochromic process in the monolayer of aphotochromic spiropyran derivative without long alkyl chain,was investigated.The photochromism at the air/water interface under differnet surface pressures was studied by surface pressure-area isotherms,surface pressure-time curves,area-time curves and Brewster angle microscopy.Both forms of the compound were found to form monolayers at the air/water interface althouhg it does not have long alkyl chain.A large area expansion in the monolayer corresponding to a zreo^th order reaction was found at the initial stage of the UV light irradiation.A series of dynamic investigations revealed that at high pressure after phase transition in the monolayer,the surface pressure changes greatly umder alternative irradiation of UV and visible light.An obvious morphological change accompanying with the photochromism was observed in situ.     

Unsymmetrical photochromic bithienylethene-bridge tetraphenylethene molecular switches: Synthesis,aggregation-induced emission and information storage

Aggregation-induced emission(AIE) active photochromic molecules have attracted growing attention for their versatile applications.Here we designed and synthesized five newly unsymmetrical photochromic diarylethene(DAE) dyads(BTE1-5) by connecting tetraphenylethene(TPE) and aromatic substituent via bithienylethene(BTE) bridge.The chemical structures of those compounds were identified by ^1H NMR,¹³C NMR and HRMS.The absorption and emission of these dyads were investigated by UV-vis and fluore scence spectroscopy,respectively.The results showed that all those compounds exhibited typically AIE or aggregation-induced emission enhancement(AIEE) characteristic.Particularly,when an aggregationcaused quenching(ACQ) fluorophore(triphenylamine) was grafted to the molecule,connecting with TPE via BTE-bridge,the ACQ phenomenon was dissipated and converted to an AIE luminophore,and those compounds exhibited photochromism upon irradiation with alternative UV and visible light.The solution or solid of those compounds showed distinctly fluorescence switching "ON" or "OFF" observation upon irradiation with alternative UV and visible light.It is interesting that BTE1 could be applied in recording and rewritable information storage,and the cyclization quantum yields could be affected by substituent significantly.     

Synthesis of Fullerene-end Functionalized Poly（methyl methacrylate） via Reverse Atom Transfer Radical Polymerization

The use of the reverse atom transfer radical polymerization （RATRP） to end-functionalize poly（methyl methacrylate） （PMMA） with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60（C70） terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques.     

THE STUDY OF PHYCOBILIPROTEINS IN Porphyra yezoensis——ASSOCIATION AND DISSOCIATION OF R-PHYCOERYTHRIN

In fresh Porphyra yezoensis, R-phycoerythrin exists mainly as octamer (αβ)_8 with only a small percentage of dimer (αβ)_2.The octamer could be dissociated into dimer in the presence of oxygen and visible light.The dimer was ultracentrifuged in a sucrose linear gradient to obtain the monomer,The monomer could be associated again into dimer.This reversible change between the monomer and dimer of R-phycoerythrin may be attributed to the shift of hydrogen bonds between forms of phycoerythrin molecules.     

Photocatalysis Activity and Physicochemical Structure of Titanium Dioxide Co-doped withN and B

Titanium dioxide co-doped with N and B was prepared by sol-gel method. The photocatalytic activity was evaluated by the photodegradation of methylene blue under visible light. Its physicochemical properties were characterized by means of UV-Vis DRS, XRD, PT-IR, and XPS. The results indicated that N-B-TiO2 has good activity to the photodegradation of MB. Its decolourizing rate of methylene blue solution goes up to 98.4% under the visible light irradiation with 5 h. The doping nitrogen forms N-Ti-O and boron primarily existing in oxide appears in the N-B-TiO2 sample. They response for visible light of TiOa was also exploited.     

Synthesis and properties of a luminescent organic material with triphenylamine and pentiptycene units

A donor–bridge–donor compound for blue light-emitting with triphenylamine as donor and pentiptycene derivative units as bridge was synthesized via Sonogashira reaction. The chemical structure was confirmed by NMR and MALDI-TOF MS. It emits blue light peaked at 442 nm with a FWHM of 59 nm in CH2Cl2. Fluorescent quantum efficiency in THF is 82% relative to 9,10- diphenylanthracene. A slight hypsochromic shift was found in its drop-cast film. Cyclic voltammetry revealed that it has high HOMO level corresponding to hole transporting character.     

Synthesis and Crystal Structure of 1-(2-Methyl-5-formyl-3-thienyl)-2-(2-methoxylphenyl)perfluorocyclopentene

A new family of photochromic diarylethene compounds, 1-(2-methyl-5-formyl-3- thienyl)-2-(2-methoxylphenyl)perfluorocyclopentene (1o) having an unsymmetrically substituted hexafluorocyclopentene unit, was synthesized and its structure was determined. The crystal belongs to the monoclinic system, space group P21/c with a = 15.4866(5), b = 9.0744(9), c = 12.6906(3), β = 90.1480(10)°, Z = 4, V = 1783.4(3)3, Dc = 1.513 mg/m3, μ = 0.25, F(000) = 824, the final R = 0.0579 and wR = 0.1566 for 2584 observed reflections (I > 2σ(I)). Interestingly, a colorless compound 1o undergoes photocyclization upon irradiation of UV light to give the blue isomer diarylethene. Upon irradiation with visible light with wavelength greater than 510 nm, the blue compound can return to its initial colorless state.     

A novel terbium complex using oxadiazole derivative as a neutral ligand： Synthesis and properties

A novel terbium complex using 1,3,4-oxadiazole derivative as a neutral ligand was synthesized and characterized. Its thermal stability and photoluminescent properties were studied. The strong emission peaked at 546 nm with a full width at half maximum of 5 nm was observed in the pure terbium complex film under excitation of 328 nm light, which is attributed to the characteristic emission of terbium ion. The good thermal stability and intense sharp emission of this terbium complex display its potential application in electroluminescence devices.     

Crystal Structure and Photochromic Properties of [1-(2-Methyl-5-(4-cyanophenyl)-3-thienyl)]-2-(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene

A new photochromic diarylethene, [1-(2-methyl-5-(4-cyanophenyl)-3-thienyl-2-(2-methyl-5-phenyl-3-thienyl)]perfluorocyclopentene(1o, C28H17F6NS2), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its crystal belongs to the monoclinic system, space group P21/c with a = 24.1381(5), b = 9.3834(6), c = 11.1073(8), β = 94.477(4)°, Z = 4, V = 2508.1(3) A3, D3 c = 1.445 mg/m, μ = 0.275, F(000) = 1112, the final R = 0.0482 and wR = 0.1429 for 5834 observed reflections(I 2σ(I)). Further study demonstrated the diarylethene underwent reversible photochromism, changing between colorless and blue in hexane solution, crystalline phase and PMMA films, respectively.     

Heterogeneous degradation of toxic organic pollutants by hydrophobic copper Schiff-base complex under visible irradiation

A hydrophobic complex of Cu2+[bis-salicylic aldehyde-o-phenylenediamine],Cu-SPA,was prepared and used as a heterogeneous photocatalyst to degrade organic pollutants in water under visible irradiation(420 nm)at neutral pH.The structure of complex was characterized by using nuclear magnetic resonance(NMR),elemental analysis,IR and UV-vis spectrometries.Degradation of Rhodamine B(RhB),Sulforhodamine B(SRB)and Benzoic acid(BA)in water were used as model reactions to evaluate the photocatalytic activities of Cu-SPA.The results indicated that RhB and SRB were easily adsorbed on the hydrophobic surface of Cu-SPA from aqueous solution(the maximum adsorption amount:Qmax=11.09 and 8.05μmol/g,respectively).Under visible irradiation,RhB and SRB were decolorized completely after 210 and 240 min,respectively,and BA was removed completely after 5 h.The efficiency of H2O2was>95%,in contrast to that of the reaction without catalyst or light(<20%).In water soluble medium,the hydrophobic Cu-SPA can be used more than 6 cycles.ESR results and the behavior of cyclic voltammetry showed that,in the reaction process,Cu2+-SPA was reduced to intermediate state Cu+-SPA firstly,which was extremely unstable and reacted rapidly with H2O2,leading to high reactive oxygen species(·OH radical)to degrade the substrate.     

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induceddoping method. In this method a copolymer of vinylidene chloride and methyl acrylate(VCMAC) was used as photo acid generator which can release proton when it is exposedto ultraviolet light (λ= 254 nm). The structure of PANI-VCMAC system before and afterirradiation was characterized by elemental analysis, IR, XPS, and SEM images. Resultsobtained indicate that the photo-induced doping characteristics, such as doping positionand type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (～10~(-5)S/cm) of PANI-VCMAC system after irradiation maybe due to low doping degree (～pH= 3) and the difference in morphology as compared withPANI-HCl film.     

PEG Assisted Hydrothermal Synthesis of β-Na YF_4:Yb~(3+),Er~(3+) Microrods for Upconversion Photoluminescence Display

β-Na YF4:Yb3+,Er3+ microrods with average length of 10 μm and diameter of 2.5 μm were synthesized through hydrothermal method. Based on the obtained microrods, transparent and flexible film with upconversion luminescence property was prepared through inorganic-organic composition method by using co-polymerization product of isobornylmethacrylate and urethane acrylate as the polymer substrate. The prepared film shows excellent optical transmission in the visible region with average transmission of 81.3% at high doping concentration(2 wt%) of β-Na YF4:Yb3+,Er3+ microrods. By directing and moving NIR laser beam toward the prepared film with high scanning speed, visible light is effectively emitted and various images are able to display.     

Photoinduced energy transfer and charge transfer on squarylium cyanine dyes

A series of squarylium cyanine dyes (Sqs) were synthesized to explore their applications in functional devices.Preliminary investigation on the mechanism involved in these devices was carried out.Spectroscopic behavior of Sqs with porphyrin (P),8-hydroxyquinolium aluminum (Alq) and ruthenium bipyridyl complex (Ru(bipy)) in solution,in film and on nanocrystalline TiO2 was investigated,respectively.A mechanism including photoinduced energy transfer and charge transfer processes was suggested in the corresponding practical devices.By means of doping,a red organic electroluminescent device (ELD) using Sq-doped Alq as the emission layer (EML) has been developed,and the total light to electricity efficiency of nanocrystalline TiO2 electrode based on using Sq-doped Ru(bipy) as photosensitizer has been improved greatly in the whole visible region,particularly in the red area above 600 nm.     

Resonance Light Scattering Spectra of Silver Thiocyanate System and its Application in Analysis

A novel determination method of Ag^＋ was established. In acetic acid-sodium acetate buffer （pH 5.0） medium, Ag^＋ reacts with SCN^- to form AgSCN in the presence of TritonX-100,which results in an increase of resonance light scattering （RLS）and giving a new RLS spectrum.The maximum RLS peak was at 585 nm,The enhancement of resonance light scattering at 585 nm was proportional to the concentration of Ag^＋ ranging from 0.0045-4.00μg mL^-1 （r=9991）,and the detection limit was 1.37 ng mL^-1 with the recovery of 97.70%- 104.80%。