Preparation and photochromism of nanocomposite thin film based on polyoxometalate and polyethyleneglycol

A photochromic nanocomposite based on Keggin structure phosphomolybdic acid (PMoA) well dispersed in polyethyleneglycol (PEG) was fabricated. TEM image showed that PMoA nanoparticles with narrow size distribution were finely dispersed in polymer matrix. FT-IR results showed that the Keggin geometry of polyoxometalates was still preserved inside the composites and strong coulombic interaction was built between PMoA and polymer matrix. Under UV irradiation, the film was reduced photochemically to yield a blue species, which was in accordance with a charge-transfer mechanism.     

Photoswitching of Ferroelectric Liquid Crystals Using Unsymmetrical Chiral Thioindigo Dopants: Photoinduced Inversion of the Sign of Spontaneous Polarization

A new unsymmetrical chiral thioindigo dopant 6‐[(R,R)‐2,3‐difluorooct‐1‐yloxy]‐5′‐nitro‐6′‐[(R)‐2‐octyloxy]thioindigo ( 4 ) designed to photoinvert the sign of spontaneous polarization (P_S) in a ferroelectric chiral smectic C (SmC*) liquid crystal was prepared using a synthetic approach previously developed in our laboratory. In this new “ambidextrous” design, the (R)‐2‐octyloxy side‐chain is sterically coupled to the thioindigo core and induces a positive P_S, whereas the (R,R)‐2,3‐difluorooctyloxy side‐chain is decoupled from the core and induces a larger negative P_S. In the trans form, this dopant induces a negative polarization in the SmC host (+)‐4‐(4‐methylhexyloxy)phenyl 4‐decyloxybenzoate ( PhB ). Irradiation of a 1 mol‐% mixture of 4 in PhB at λ = 510 nm caused a sign inversion of P_S, from –0.88 to +0.42 nC cm^–2 at T – T_C = –5 °C, which is consistent with an increase in the polarization power of the coupled 2‐octyloxy/thioindigo unit over that of the 2,3‐difluorooctyloxy unit, due to the increase in transverse dipole moment of the thioindigo core upon trans–cis photoisomerization. The P_S sign inversion was confirmed by a surface‐stabilized ferroelectric liquid crystal photoswitching experiment. Spectroscopic measurements on films of the doped liquid crystal mixtures showed that trans–cis photoisomerization is gradually suppressed with increasing dopant mole fraction, possibly as a result of increased dopant aggregation.     

Imidazole-based dithienylethenes as a selective chemosensors for iron(III) ions

Four novel imidazole-based dithienylethenes have been successfully synthesized in good yields. Their structures have been confirmed by NMR spectrometry, mass spectrometry, and elemental analyses. UV/Vis absorption spectra indicated that these dithienylethenes can easily isomerize between the open-ring and closed-ring isomers upon irradiation with UV or visible light in solution, and that the respective closed-ring isomers show decreased fluorescence properties compared with the open-ring isomers. Moreover, the open-ring and closed-ring isomers display high selectivity toward Fe³⁺, such that the addition of Fe³⁺ obviously suppresses their fluorescence intensity.     

A novel photochromic material based on halophosphate: Remote light-controlled reversible luminescence modulation and fluorescence lifetime regulation

Luminescent material Ca₂Ba₃(PO₄)₃F:Eu²⁺ displays green emitting in the range of 400–700?nm, which is ascribed to the 4f⁶5d¹ →4f⁷ transition of Eu²⁺ ions. Amazingly, the body color of the samples can be changed between colorless and green upon alternative UV and visible light irradiation/heating treatment with robust fatigue resistance due to photochromism. The photochromic effect strongly depends on the Eu²⁺ doping concentration. After remote-controlled short-UV irradiation, the overall Eu²⁺ emission intensity presents a significant decrease, and inversely, exhibits an increase to the initial level after illuminated by longer wavelength light or heat treatment. Moreover, the fluorescence lifetime also can be regulated reversibly, of which the regulation degree depends on the short-UV irradiation and longer wavelength illumination time/heating temperature. A schematic diagram based on energy levels is proposed to illustrate the photochromism mechanism.     

Properties of photochromic retinals

In the present review, we summarize our recent studies on the synthesis and spectral-kinetic parameters of photochromic retinals based on spiropyrans, diarylethenes, and a fulgimide and the use of these compounds for the preparation of artificial analogs of natural bacteriorhodopsin.     

Spiropyran, chromene and spirooxazine, mélange á trois: Molecular logic systems through selective and reversible deactivation of photochromism mediated by CO2 gas

We report a new expanded molecular logic system based upon combinations of spiropyrans, spirooxazines and chromenes, whereby the photochromism of some molecules can be selectively preserved while reversibly deactivating the photochromism of others. The non-photochromic molecules can be reversibly activated by CO₂ gas. It was found that the photochromic effect of spiropyrans, in general, and one spirooxazine (with a hydroxyl group on the naphtho-ring) could be reversibly deactivated by DBU, while a chromene and an unsubstituted spirooxazine remained photochromic in the system under the same conditions. The presence of protic solvent was necessary for the deactivation of some of these photochromic molecules and hence it was used as an additional sensitizer in the system. This afforded the expansion of stimuli for molecular logic operations and allowed combinations of the benign stimuli of UV, visible light, CO₂, and CO₂ depleted with protic and aprotic solvents. This effect provided the mechanism for molecular logic systems that do not suffer from the usual problems of dilution effects and hence become truly reversible. This is highly significant when designing molecular switches to perform logic operations.     

Phosphor SrZrO3:Sm3+ with fluorescence modulation and photochromic characteristics for erasable optical storage

At present, for inorganic photochromic materials, the single function limits their application level in the field of optical storage and anti-counterfeiting. Generally, the reversible modulation of photoluminescence is achieved through a photochromic process, thereby improving the ability of the photochromic material to store information. Here, we designed a Sm³⁺ doped perovskite oxide (SrZrO₃:Sm³⁺) inorganic photochromic material. Combined with its red photoluminescence and photochromic properties, it can realize dual information storage and recognition functions. The fluorescence regulation function is realized by the doping of Sm³⁺, which is conducive to the application in the direction of optical switch. The mechanism of photoluminescence and photochromism was studied. Finally, a flexible film with SrZrO₃:Sm³⁺ material was fabricated to demonstrate rewritable optical recording and storage and reading of dual optical information.     

Luminescence modulation of the Eu3+ doped Srn+1SnnO3n+1 (n=1, 2, 5, ∞) ceramics based on photochromism and its application in anti-counterfeiting technology

The structure and optical properties of Sr_n+1Sn_nO_3n+1 ceramics greatly depend on the n value. Thus, we fabricated four compositions, namely Sr_n+1Sn_nO_3n+1:Eu³⁺ (n = 1, 2, 5, ∞) ceramics, and their crystal structure, photoluminescence, photochromism and luminesce modulation properties have been investigated. It is found that excellent photochromism and luminesce modulation properties are found in Sr₂SnO₄:Eu³⁺ and Sr₃Sn₂O₇:Eu³⁺ ceramics. After 280-nm light irradiation, the Sr₂SnO₄:Eu³⁺ ceramics transform into gray purple from primal white. Meanwhile, luminescence intensity decrement ratio ΔI_dec of the colored Sr₂SnO₄:Eu³⁺ reaches a high value of 80.8% under optimized irradiation wavelength. The decreased luminescence intensity of Eu³⁺ can be completely recovered via 450-nm light irradiation. The ΔI_dec of Sr₃Sn₂O₇:Eu³⁺ ceramic reaches 53.1%, and the decreased luminesce intensity can not be covered by light irradiation, only can be covered by a high temperature stimulus at 400 °C. Finally, we successfully fabricated a flexible membrane using Sr₂SnO₄:Eu³⁺ and PDMS for anti-counterfeiting applications.     

Stress in photochromic and electrochromic effects on tungsten oxide film

Optical absorbance at 632.8 nm and the stress generated in tungsten oxide film due to photochromic and electrochromic effects were measured. WO₃ thin films were deposited by reactive sputtering and the absorbance was obtained by measuring the optical transmittance of a laser beam through the film. The stress was calculated by measuring the substrate curvature and using the Stoney equation for multilayered films, since two layers are deposited onto a substrate for the electrochromism studies. The optical absorbance and the stress in the tungsten oxide film, as a function of UV irradiation time in photochromism and of inserted charge in electrochromism, are showed and discussed. In both effects the stresses generated were rendered as due to cation insertions into the film: H⁺ protons in photochromism and Li⁺ ions in electrochromism. The accuracy of the Stoney equation used for the stress calculation was also discussed.