Photochromic Properties Research Articles

A donor-acceptor π-stacked multifunctional Eu-MOF based on a novel viologen-like photosensitive ligand: Degradation of tetracycline, photochromism, and photoluminescence

The photosensitive building blocks of photochromic MOFs are mostly 4,4′-bipyridine. However, the linear structure and kind of 4,4′-bipyridine derivatives limit the development of its properties and applications. Therefore, a “Y"-shaped 2,4,6-tri (4-pyridyl)-1,3,5-triazine derivative ([H3p-Batpt]Cl3, TPT) with high conjugation, bare nitrogen and oxygen sites that was selected as a novel photosensitive ligand to replace the traditional 4,4′-bipyridine ligand for photochromic MOFs. Then, [H3p-Batpt]Cl3 was combined with EuIII and terephthalic acid (H2TPA) to construct a multifunctional Eu-MOF [Eu2 (p-Batpt) (TPA)3(H2O)]n (1). 1 possess degradation of tetracycline (TC), photochromic and photoluminescence properties. The colored 1 (1P) after irradiation with UV–vis light (300 W, Xe-lamp) is difficult to fade due to donor-acceptor (D-A) π-π and radical-π interactions. In addition, 1 is used in photocatalysis because it is an excellent N-type semiconductor. The TC degradation rate of 1 can reach 67.42 % under visible light and be recycled six times. Interestingly, the TC degradation rate of 1P was 6.78 % higher than that of 1. Electrochemical tests show that 1P has higher charge separation efficiency and a smaller band gap. The free radicals capture and ESR experiments of 1 revealed that holes (h+) played a leading role in the photocatalytic degradation of TC. This research expands the application of photochromic MOFs and provides a reference for removing organic pollutants.

Aza-Diarylethenes Undergoing Both Photochemically and Thermally Reversible Electrocyclic Reactions.

Exploring novel molecular photoswitches plays a crucial role in the field of photo-functional materials chemistry. In this study, we synthesized aza-diarylethenes with benzothiophene-S,S-dioxide as apart of hexatriene structureand investigated their photochromic properties. Unlike previously reported aza-diarylethenes, which exhibit fast thermally reversible photochromism, the compounds synthesized here exhibited pseudo-photochemically reversible photochromism. Due to their thermal stability, we successfully isolated the colored isomer. X-ray crystallographic analysis revealed for the first time that the colored isomer adopts a closed-ring structure with a bond between carbon and nitrogen atoms. Remarkably, these aza-diarylethenes exhibited not only photochemical ring-closing and ring-opening reactions but also thermal ring-closing and ring-opening reactions, driven by a thermal equilibrium between the open- and closed-ring isomers. This behavior, unprecedented for common diarylethenes, was elucidated through kinetic analysis, revealing an energy-level diagram for the thermal equilibrium between these isomers. Furthermore, 1H NMR spectroscopy revealed that both photochemically and thermally generated closed-ring isomers adopt the same structure, which was well explained based on the reaction mechanism of photochemical and thermal ring-closing reactions. These findings not only advance the field of aza-diarylethenes but also inspire future research in the development of new photoswitches.

Engineering Supramolecular Hydrogels via Reversible Photoswitching of Cucurbit[8]uril-Spiropyran Complexation Stoichiometry.

The integration of photoswitchable supramolecular units into hydrogels allows for spatiotemporal control over their nanoscale topological network and macroscale properties using light. Nevertheless, the current availability of photoswitchable supramolecular interactions for the development of such materials remains limited. Here, the molecular design of a novel photoswitchable cucurbit[8]uril-spiropyran host-guest complex exhibiting fast and reversible switching of binding ratios between 1:2 and 1:1 is reported. Photoswitchable complexation stoichiometries are rationally exploited as (de)crosslinking units in multiple polymers for the design of supramolecular hydrogels displaying highly dynamic and switchable features that are spatiotemporally controlled by light. The hydrogels exhibit rapid reversible mechanical softening-hardening upon alternating irradiation with blue and UV light, which is used to significantly accelerate and improve the efficiency of self-healing and shape-remolding of hydrogels. Furthermore, spiropyran endows such materials with unique reversible photochromic properties for reproducible patterning/erasing and information storage. Using a dual-light-assisted extrusion process, meter-scale hydrogel fibers with enhanced structural integrity and photoswitchable ionic conductivity are constructed and woven into various slidable knots and fluorescent shapes. This work represents an innovative molecular design strategy for advancing the development of spatiotemporally engineered supramolecular hydrogels using light and opens avenues for their prospective applications in dynamic materials and adaptive systems.

Orthogonal Photo‐ and Thermo‐Responsive Fluorescent Polymeric Hydrogels for Multi‐Level Information Encryption and Anti‐Counterfeiting

AbstractStimulus‐responsive fluorescent polymeric materials (FPMs) that can change their fluorescent states via external stimuli have been widely applied in multi‐level information encryption and anti‐counterfeiting. While many efforts have mainly focused on the design of dual‐stimuli responsive FPMs, the construction of orthogonal photo‐ and thermo‐regulation of fluorescent polymeric systems remains a challenge. Here, the orthogonal photo‐ and thermo‐responsive fluorescent polymeric hydrogels (PTFPHs) containing capsules with the phase change materials (PCMs), photoresponsive molecules (DTE), and thermally responsive molecules (TPA‐DCPP) are reported. They are capable of reconfiguring fluorescence (none, green, yellow, red) via photo‐ and thermo‐induced fluorescence resonance energy transfer (FRET) process. Additionally, not only can the thermochromic property of PTFPHs be regulated by modulating the composition of PCMs, but the thermochromic and photochromic properties of PTFPHs can also be tuned by using SDS to control the size of capsules. The developed hydrogels exhibited high fluorescence contrast, fast response, and excellent reversibility. The PTFPHs are successfully applied in multi‐level information encryption and integrated application between temperature monitoring and anti‐counterfeiting. The works represented a strategy for developing multi‐stimuli responsive PTFPHs in multi‐level information encryption and advanced anti‐counterfeiting.

Synthesis, structure, and photochromic properties of Zn-coordination polymers derived from hexyl viologen cations

This study presents the synthesis, structural characterization, and investigation of the photochromic properties of two Zn-coordination polymers, formulated as {(HV)0.5[Zn(MIC)(HMIC)]·H2O}n (1) and {(HV)2[Zn4(BTEC)3]}n (2) (H2MIC = 5-methylisophthalic acid, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid, HVBr2 = 1,1′-bis(n-hexyl)-4,4′-bipyridinium dibromide), derived from hexyl viologen cations. Compound 1 is characterized by a one-dimensional (1D) structure, while compound 2 exhibits a three-dimensional (3D) architecture, both crystallizing in distinct space groups and showcasing unique assembly and composition. Detailed structural analysis reveals the coordination modes of Zn(II) ions within these polymers. The photochromic behavior of two compounds under UV light exposure was thoroughly examined through ultraviolet-visible (UV–vis) and electron paramagnetic resonance (EPR) spectroscopy, demonstrating reversible color changes from light yellow to blue upon irradiation, with distinct rates of decolorization indicative of the stability of photo-induced viologen radicals. This reversibility was successfully replicated over multiple cycles, underscoring the durability of the photochromic transition. Furthermore, powder X-ray diffraction (PXRD) data confirmed the maintenance of crystal structures throughout the photochromic process, dismissing photolysis or photo-induced isomerization as underlying mechanisms. Instead, the observed photochromism is attributed to efficient electron transfer facilitated by the proximity between electron-donating and electron-withdrawing groups within the coordination polymers. This study highlights the influence of structural parameters on the photochromic properties of viologen-based coordination polymers, offering insights into the design of photo-responsive materials.

Binder-enhanced reversible photochromic films by tungsten oxide hybrid composites for advanced applications

In this study, we developed binder-enhanced reversible photochromic tungsten oxide (WO3) films for advanced applications. Expanding on previous research, we used tungsten oxide hybrid composites as the base material and incorporated various binders, specifically polyethylene glycol (PEG), polysorbate 80 (PS 80), and carboxymethyl cellulose (CMC), to evaluate their effects on reversible photochromic reactions. Our experiments demonstrated that the inclusion of CMC significantly improved the photochromic properties and exhibited the fastest reversible reactions when compared to PEG and polysorbate 80. This enhancement is attributed to the high density of hydroxyl groups and the network structure of CMC, which facilitate efficient proton transfer and oxygen permeability, both crucial for the reoxidation process in WO3. Density functional theory (DFT) calculations supported these findings by indicating that CMC has a suitable bandgap and electron mobility, which enhance charge injection and transport. Additionally, the fabricated films showed consistent and stable performance under both heat treatment and natural ambient conditions. These results underscore the potential of CMC as an effective binder for developing high-performance, reversible photochromic films suitable for applications in smart windows, displays, and optoelectronic devices.

Antiswelling Photochromic Hydrogels for Underwater Optically Camouflageable Flexible Electronic Devices.

Optical camouflage offers an effective strategy for enhancing the survival chances of underwater flexible electronic devices akin to underwater organisms. Photochromism is one of the most effective methods to achieve optical camouflage. In this study, antiswelling hydrogels with photochromic properties were prepared using a two-step solvent replacement strategy and explored as underwater optically camouflaged flexible electronic devices. The hydrophobic network formed upon polymerization of hydroxyethyl methacrylate (HEMA) ensured that the hydrogels possessed outstanding antiswelling properties. Internetwork hydrogen bonding interactions allowed the hydrogels to exhibit tissue-adaptable mechanical properties and excellent self-bonding capabilities. The introduction of polyoxometalates further enhanced the hydrogels' mechanical and self-bonding properties while imparting photochromic capability. The hydrogels could be rapidly and reversibly colored under 365 nm UV irradiation. The bleaching rate of the colored hydrogels increased with temperature, bleaching within 12 h at 60 °C but maintaining the color for more than 5 days at room temperature. The self-bonding and photochromic properties enabled the hydrogels to be easily assembled into optically camouflaged underwater flexible electronic devices for underwater motion sensing and wireless information transmission. An optically camouflaged strain sensor was first assembled for underwater limb motion sensing. Additionally, an underwater optically camouflaged wireless information exchange device was assembled to enable wireless communication with a smartphone. This work provided an effective strategy for the optical camouflage of underwater flexible electronic devices, presenting opportunities for next-generation underwater hydrogel-based flexible devices.

Defect engineering by annealing: Managing the trade-off relationship between photochromic and electrical properties in KNN-based translucent ceramics

Rare-earth-doped transparent ferroelectrics exhibit outstanding optical transparency, photoluminescence (PL), photochromic (PC) and various electrical properties, showing potential for use in optoelectronic applications. However, there is an inevitable trade-off relationship between optical and electrical coupling during the integration of multifunctionality. In this work, Ba2+, Ho3+ and Yb3+ were codoped in KNN translucent-ferroelectric ceramics (as a model material) to overcome the contradiction between optical (transparency/PC) and electrical properties (resistivity/ferroelectricity). The defects (mainly oxygen vacancies) within the ceramics can be effectively regulated through annealing under different atmospheres. At the cost of a slight decrease in PC performance, the electrical properties significantly improved; i.e., for the optimal ceramic annealed in an oxygen atmosphere, both the maximum and remnant polarizations nearly doubled, and the resistivity significantly decreased compared to that of the original sample. A mechanism for regulating these properties was proposed. This research serves as a valuable example for adjusting the optical and electrical properties of other ferroelectrics through annealing.

Multimodal anti-counterfeiting and optical storage application based on luminescence reversible modification and color change of photochromic phosphor

Reversible upconversion luminescence (RUCL) modification based on photochromism has received considerable interest due to its potential applications in optical storage and invisible optical anti-counterfeiting. Herein, white β-Ba2ScAlO5: Yb3+, Er3+ (β-BSAO-YE) phosphor was irradiated with 254 nm light, which caused the phosphor to turn blue due to the increase of oxygen vacancy. The blue β-BSAO-YE phosphor returns to its original color upon stimulation with 808 nm laser light or 125 °C, exhibiting a double photo-induced reversible photochromic change. The green and red upconversion luminescence (UCL) of the β-BSAO-YE were reversibly modified according to their photochromic properties. The UCL modification changes the luminescence color of the pattern, indicating that β-BSAO-YE phosphor is an ideal compound anti-counterfeit agent. The light information recorded on the β-BSAO-YE binary photochromic dot matrix can be read under ultraviolet (UV) and near-infrared (NIR) excitation, demonstrating the potential application of β-BSAO-YE phosphors as optical data storage media. In addition, the cyclic experiment showed good photochromic and UCL modulation repeatability. The new luminescent β-BSAO-YE not only proposes a new way to exploring upconversion red light materials, but also provides new materials for optical storage, optical information and optical anti-counterfeiting.

Reversibly photochromic wood constructed by electric field-assisted self-assembled chitosan and tungsten trioxide coatings

ABSTRACT The photochromic properties are highly desirable for advanced wood applications, but they have not been extensively studied. To incorporate photochromic capabilities into wood materials, composite coatings were developed on the wood surface using an electric field-assisted layer-by-layer (LBL) self-assembly technique. The composite coatings consist of cationic chitosan and anionic tungsten trioxide (WO3) nanoparticles. By applying a direct current voltage during the deposition process, a well-organized distribution of WO3 nanoparticles was achieved, resulting in a uniform coverage of the wood substrate. This assembly process facilitated the creation of structured photochromic coatings with minimal nanoparticle fillers, a straightforward and rapid procedure, and potential for large-scale production. Lab colorimetric results demonstrated that the wooden substrate changed color from its natural state to blue when exposed to UV light. UV-vis spectroscopy further confirmed the efficient absorption of WO3 and photochromic properties of the modified wood.

Efficient Reversible Upconversion Luminescence Modulation based on Photochromism of Lanthanides‐Doped BaMgSiO4 Glass Ceramics Toward Optical Storage Application

AbstractTransparent glass with photochromic and luminescent properties has recently garnered considerable interest in optical storage, while the photochromic transparent glass system is still limited. Herein, it is proposed that combining transparent glass matrix with photochromic nanocrystals is an efficient strategy to develop a broader range of photochromic luminescent glass systems. The Yb3+/Tb3+ co‐doped BaMgSiO4 glass ceramics are successfully prepared by a two‐step melt‐quenching approach followed by a thermal treatment in a reducing atmosphere. The glass ceramics exhibit high transparency and distinct coloration, showing a color change between colorless and pink by alternating irradiation between 365 nm ultraviolet light and 473 nm laser. The formation of color centers in the BaMgSiO4 nanoparticles drives the coloration of such glass ceramics. Based on their photochromic and photobleaching behavior, the efficient reversible upconversion luminescence modulation can be implemented with the maximum luminescence modulation rate of 79.83%. The excellent reproducibility and anti‐fatigue of such upconversion luminescence modulation demonstrate the promising application of Yb3+/Tb3+ co‐doped BaMgSiO4 glass ceramics as an optical storage medium.

Grafting photochromic spiropyran polymer brushes on natural rubber surface via surface-initiated ring-opening metathesis polymerization

The modification of stereoregulated functionalized polymers on the surface of natural rubber (NR) is a challenging task. This work provided a practicable grafting method to design photochromic polymer brushes on the NR surfaces using surface-initiated ring-opening metathesis polymerization (SI-ROMP). The designed photochromic polymer brushes were based on norbornenes with spiropyrin (SP) pendents, and grew from the surface of NR films in the presence of Grubbs 2nd catalyst. The results showed that the grafting rate of polymer brushes with photoisomerization structure reached up to 44.91 %. The modified natural rubber (NR-SP) films exhibited rapid coloring/decolorization property under UV irradiation and visible light. This photochromic property initiated by the light-induced isomerisation of the spiropyran structure and the increased surface energy under light stimuli. NR-SP films exhibited stable photochromic characteristics and outstanding anti-fatigue properties after exposing to over six cycles of consecutive UV/Vis irradiation. A simple and practical strategy for the preparation of highly sensitive photochromic natural rubber materials is proposed and provides a potential application in the fields of information storage and anti-counterfeiting.

Synthesis, photochromic, and cytotoxic properties of water-soluble spiropyran containing an ammonium group

Synthesis, photochromic, and cytotoxic properties of water-soluble spiropyran containing an ammonium group

Stepwise Photochromism of Large Macrocycles Incorporating Two Negative Photochromic Units.

Macrocyclic photochromic molecules incorporating multiple photochromic units are known to exhibit cooperative and nonlinear photochromic reactions among distinct photochromic components. While extensive research has concentrated on positive photochromic molecules, this study presents a pioneering attempt in synthesizing macrocyclic photochromic molecules that integrate negative photochromic units. Binaphthyl-bridged phenoxyl imidazolyl radical complex, BN-PIC, exhibits unique negative photochromism in which the thermally stable colored isomer converts to the metastable colorless isomer via a short-lived biradical upon visible-light irradiation. Macrocyclic biphotochromic molecules incorporating two BN-PIC units were synthesized and the effects of ring strain on the photochromic properties including the photoconversion efficiencies and the rates of the thermal reverse reaction were investigated. The photokinetic study of these macrocyclic biphotochromic molecules demonstrated that the structural distortion of the ring caused by the isomerization of one photochromic unit significantly influenced the photoisomerization efficiency and the rate of the thermal reverse reaction of the other photochromic unit.

Effects of H vacancies on photochromic properties of oxygen-containing yttrium hydride

We present in-situ studies of H loss from YHO films using ion beam analysis and its effect on the photochromic properties. The film evaporates loosely bound H under exposure to a beam of 3056 keV He2+ without a concomitant increase of O. Annealing at 145 °C decreases both the photochromic contrast and the bleaching speed indicating the importance of mobile H for the photochromic reaction.

Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation.

The ability to correlate the structure of a molecule with its properties is the key to the rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of the metastable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The lack of synthetic techniques to derivatize the abundant parent dye and a thorough understanding of the impact of structural factors on the photochemical and thermal properties hinder broad applications of this emerging photoswitch class. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for monoarylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N'-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N'-alkyl groups enable the independent attachment of functional moieties without affecting the photochromic properties. A strong correlation between the structure of the N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules.

Two multifunctional Eu-MOFs with dual photochromic and luminous centers for multiple optical switches and anti-counterfeiting properties

In this work, two multifunctional Eu-MOFs with dual photochromic and luminous centers, formulated as Eu3[(ipbp)4·6H2O]·3H2O (1) and Eu[(ipbp)·(p-BDC)·H2O] (2) (ipbp = 1-(3,5-isophthalic acid)-4,4′-bipyridine chloride, p-BDC = terephthalate), were successfully constructed by solvothermal reactions. The carboxylate pyridine ligand gives the two frameworks excellent photochromic properties, while the metal europium endows the two compounds splendid luminous properties. In addition, the application of the two compounds in three kinds of optical switches is further demonstrated. Finally, the two compounds with dynamic multicolor anti-counterfeiting properties were also explored. This work not only proposed bicentric light-emitting and color-changing materials, but also provided a new strategy for studying multiple optical switches and dynamic anti-counterfeiting.

Innovative Synthesis of Photo-Responsive, Self-Healing Silicone Elastomers with Enhanced Mechanical Properties and Thermal Stability.

Photo-responsive materials have garnered significant interest for their ability to react to non-contact stimuli, though achieving self-healing under gentle conditions remains an elusive goal. In this research, an innovative and straightforward approach for synthesizing silicone elastomers is proposed that not only self-heal at room temperature but also possess unique photochromic properties and adjustable mechanical strength, along with being both transparent and reprocessable. Initially, aldehyde-bifunctional dithiophene-ethylene molecules with dialdehyde groups (DTEM) and isocyanurate (IPDI) is introduced into the aminopropyl-terminated polydimethylsiloxane (H2N-PDMS-NH2) matrix. Subsequently, palladium is incorporated to enhance coordination within the matrix. These silicone elastomers transition to a blue state under 254nm UV light and revert to transparency under 580nm light. Remarkably, they demonstrate excellent thermal stability at temperatures up to 100°C and show superior fatigue resistance. The optical switching capabilities of the silicone elastomers significantly affect both their mechanical characteristics and self-healing abilities. Notably, the PDMS-DTEM-IPDI-@Pd silicone elastomer, featuring closed-loop photo-switching molecules, exhibits a fracture toughness that is 1.3 times greater and a room temperature self-healing efficiency 1.4 times higher than its open-loop counterparts. This novel photo-responsive silicone elastomer offers promising potential for applications in data writing and erasure, UV protective coatings, and micro-trace development.

Naphthalene-embedded spiropyran derivative-A type of conjugated expanded material with solid-state photochromic properties and tunable color switching range

Due to the limited free volume in the solid state, spiropyrans generally exhibit photochromic properties in solution or mixed thin films. However, few spiropyrans can display the photoisomerization process in the solid state. One conventional solution for solid-state photochromism is to embed the spiropyran on polymer chains or introduce bulky groups to create an efficient free volume in the solid state. In this article, we attempt to introduce large conjugated fragments on the spiropyran backbone to construct a donor-acceptor (D-A) building block that not only possesses an enlarged π-electron system with enhanced electronic delocalization capability but also exhibits an improved free volume for efficient solid-state photoisomerization. Through this strategy, we have successfully embedded the naphthalene ring on the spiropyran backbone to obtain a novel D-A type conjugated building block, SP-Naph, which exhibits excellent solid-state photochromic performance and reversibility. Furthermore, the D-A structure of SP-Naph significantly tuned its photochromic color-switching range to blue. Consequently, SP-Naph was successfully applied in optical printing and invisible inks. The excellent solid photochromic properties make it exhibit remarkable photochromic effects, indicating significant potential for optical printing and anti-counterfeiting applications.

Delignification of wood toward photoluminescent smart window infiltrated with glass nanofibers-reinforced polystyrene for multifunctional applications

Multifunctional photochromic and fluorescent woods that can change their color in the presence of ultraviolet light were developed. A formulation of electrospun glass nanofibers-reinforced styrene as a hosting agent and rare-earth strontium aluminate (RSA) as a photoluminescent was infiltrated into a lignin-modified wooden substrate, resulting in translucent wood with fluorescence and photochromic properties. The RSA pigment is known for its good photostability and thermal stability. An ideal method for producing transparent photoluminescent wood involves dispersing the RSA phosphor in pre-polymerized glass nanofibers-reinforced styrene without aggregation. According to the colorimetric data from the CIE (Commission Internationale de l´Eclairage) Lab color space coordinates, this photoluminescent wood substrate became green when exposed to ultraviolet light, but remained colorless when exposed to visible light. Electron microscopic images were used to investigate the morphologies of the synthesized pigment nanoparticles (NPs) and electrospun glass nanofibers, displaying diameters of 5–15 nm and 50–100 nm, respectively. The photoluminescent woods were inspected with different microscopic and spectroscopic techniques, including energy-dispersive X-ray spectroscopy (EDX), X-ray fluorescent spectroscopy (XRF), and scanning electron microscopy (SEM). Upon excitation at 365 nm, the photoluminescence transparent timbers demonstrated an emission intensity at 519 nm. When increase the phosphor content, the produced luminous wood was monitored to be more water-resistant and had better protection from ultraviolet rays. The reaction of the transparent luminous wood to ultraviolet light was rapid and reversible without fatigue.