Photoinduced Color Research Articles

Crystal structure and photochromic properties of three cocrystals derived from 1,1′-bis(carboxymethyl)-4,4′-bipyridine

Three cocrystals synthesized from 1,1′-bis(carboxymethyl)-4,4′-bipyridine (BCMbpy) have been developed: (H2BCMbpy)0.5(H2BTEC)0.5·(H4BTEC)0.5·2H2O (1), (BCMbpy)0.5·(H2TPDC)·H2O (2), and (BCMbpy)·(H4BTEC)·2H2O (3) (where H4BTEC is 1,2,4,5-benzenetetracarboxylic acid and H2TPDC is thiophene-2,5-dicarboxylic acid). The crystal structures and photochromic properties of the three cocrystals were investigated. All three compounds exhibit reversible electron transfer (ET) photochromic behavior, reverting to their original colors in darkness. Notably, compound 3 demonstrates both intramolecular and intermolecular ET modes. The response rates for photoinduced color changes are ranked as 3 > 1 > 2, which is influenced by the steric and electronic structures of the compounds. This indicates that the balance between ET and resultant photochromism can be achieved through the careful modulation of electron acceptors and donors.

Femtosecond laser writing of robust waveguides in optical fibers with enhanced photosensitivity

We report the femtosecond laser writing of meter-long optical waveguides inscribed through the coating of specifically designed optical fibers. In order to improve the material photosensitivity and to ensure non-guiding optical fibers for subsequent laser processing of the waveguiding core, a depressed refractive index core design is implemented by co-doping a large portion of the optical fiber with germanium oxide and fluorine. The enhanced photosensitivity provided by further deuterium loading these fibers allows laser-writing of large refractive index contrast waveguides over wide cross sections. To mitigate the formation of photoinduced color centers causing high propagation losses in the photo-written waveguides, thermal annealing up to 400°C is performed on polyimide-coated laser-written fibers. Although the refractive index contrast decreases, the propagation losses are drastically reduced down to 0.08 dB/cm at 900nm allowing a robust single-mode guiding from visible to near infrared. Our results pave the way towards the development of a new generation of optical fibers and photonic components with arbitrarily complex designs.

Photo- and Oxygen- Synergistically Controlled Selective Expression of Organic Phosphorescence Units.

Dynamic control of ultralong organic room-temperature phosphorescence (UORTP) is a charming target. Herein, we report a stimuli-responsive phosphorescence unit 7H-indolo[2,3-c]quinoline (NBCz) and its derivatives (PCBNBCz, FSO2NBCz, and N2BCzSO2NBCz) that show photo- and oxygen- synergistically induced afterglow activation and afterglow color change in the PMMA film. PCBNBCz and FSO2NBCz feature a donor-acceptor (D-A) structure, and N2BCzSO2NBCz features acceptor-bridged two different phosphorescence units (NBCz and N2BCz). The photoactivated UORTP of PCBNBCz and FSO2NBCz arises from the photoinduced consumption of oxygen in the PMMA film. It is clear that the phosphorescence unit NBCz contributes to subsequent photoinduced UORTP color change because the NBCz-doped PMMA film shows the same UORTP color change process. ESR and HRMS measurements confirmed that oxidation of NBCz occurs at the nitrogen atom of the quinoline ring via photogenerated superoxide radicals, which results in the UORTP color change. TDDFT calculations proved that after oxidation of NBCz, the T1 energy level declines significantly. Furthermore, photocontrolled selective expression of phosphorescence units is achieved in the case of N2BCzSO2NBCz. After further UV irradiation, oxidation of NBCz happened, and the oxidized form N2BCzSO2NBCz-O emitted the intrinsic orange UORTP of NBCz-O selectively and screened the intrinsic yellowish-green UORTP of N2BCz. Finally, multilevel photolithography can be demonstrated based on the photoactivated UORTP and the photoinduced UORTP color change. This work may give a deep insight into organic phosphorescence and pave a simple way for the development of stimulus-responsive smart UORTP materials.

Photo-induced coloration and reversible luminescence modulation based on phosphosilicate glass ceramics for optcal storage application

Photochromic luminescent glass-ceramics attract lots of attention as an optical storage medium owing to their large storage capacity, reversible luminescence modulation, simple operation, etc. Herein, a kind of phosphosilicate glass containing AgBr nanoparticles was designed and prepared, which can realize the color reversible transformation between light yellowish-green and brown by alternating 365 nm light illumination and thermal treatment at 300 °C. The mechanism of photochromism and bleaching of the glass is related to the generation and decomposition of Ag0 clusters. Relying on the re-absorption effect, the emission intensity of Eu3+ ions could be reversibly regulated, showing the maximum luminescence contrast of 74 %. A good fatigue resistance and reproducibility of transmittance and luminescence modulation could be observed in cycle measurements, demonstrating its potential in the optical memory field.

Metal–cyanide hybrid materials exhibiting photochromic and photomagnetic responses based on viologen receptors

A photochromic material based on viologen was synthesized. During the photo-induced color transition, the DC magnetic susceptibility was enhanced by 48%, and an increase in the magnetic relaxation time after illumination was observed.

Photoluminescent Microbit Inscripion Inside Dielectric Crystals by Ultrashort Laser Pulses for Archival Applications.

Inscription of embedded photoluminescent microbits inside micromechanically positioned bulk natural diamond, LiF and CaF2 crystals was performed in sub-filamentation (geometrical focusing) regime by 525 nm 0.2 ps laser pulses focused by 0.65 NA micro-objective as a function of pulse energy, exposure and inter-layer separation. The resulting microbits were visualized by 3D-scanning confocal Raman/photoluminescence microscopy as conglomerates of photo-induced quasi-molecular color centers and tested regarding their spatial resolution and thermal stability via high-temperature annealing. Minimal lateral and longitudinal microbit separations, enabling their robust optical read-out through micromechanical positioning, were measured in the most promising crystalline material, LiF, as 1.5 and 13 microns, respectively, to be improved regarding information storage capacity by more elaborate focusing systems. These findings pave a way to novel optomechanical memory storage platforms, utilizing ultrashort-pulse laser inscription of photoluminescent microbits as carriers of archival memory.

Photochromic, fluorescence modulation and inkless printing of a zinc(II) inorganic–organic hybrid material based on 2,3-pyridinecarboxylic acid

An inorganic–organic hybrid material [Zn(2,3-pydc)(H2O)2]n (1) was synthesized with 2,3-pyridinecarboxylic acid (2,3-H2pydc) and Zn(NO3)2·6H2O by solvothermal method. Compound 1 exhibits reversible photochromism between pale yellow and blue. The electron-transfer photochromism of 1 was verified by UV–vis, EPR and XPS spectra. The electron was transferred from carboxylate to pyridine ring upon irradiation. It is worth noting that unlike the luminescence quenching of normal photochromic materials via photoinduced coloration, the emission intensity of 1 can be obviously enhanced in the process of electron-transfer photochromism. 1 was found to display a long charge-separated state with a lifetime value of more than 6 months, exceeding the most reported values of the analogues. It endows potential to be applied in inkless printing.

Photo-induced self-reduction enabling ultralow threshold voltage energy-conservation electrochromism

Electrochromic (EC) devices are highly desired for fields like smart windows, sensing, and display because of their great light modulation ability. However, the high driving voltage of the EC device usually leads to the decomposition of internal electrolyte, degradation of cyclability and higher energy consumption. In this work, based on the finding of the photo-induced self-reduction and coloration of light illuminated viologen/TiO2 gels (VTGs), we develop VTG-based devices which show remarkable EC performance under an ultralow voltage (∼0.1 V). The working energy consumption of a VTG device is at least one order of magnitude lower than those of reported EC devices and other display technologies, giving rise to the larger area/scale optical modulation. Furthermore, through the construction of RGB array displays, large-area EC devices, and flexible EC devices, the universal applicability and multifield potential applications of VTGs were demonstrated.

Photocontrolled multiple-state photochromic benzo[b]phosphole thieno[3,2-b]phosphole-containing alkynylgold(I) complex via selective light irradiation

Photochromic materials have drawn growing attention because using light as a stimulus has been regarded as a convenient and environmental-friendly way to control properties of smart materials. While photoresponsive systems that are capable of showing multiple-state photochromism are attractive, the development of materials with such capabilities has remained a challenging task. Here we show that a benzo[b]phosphole thieno[3,2‑b]phosphole-containing alkynylgold(I) complex features multiple photoinduced color changes, in which the gold(I) metal center plays an important role in separating two photoactive units that leads to the suppression of intramolecular quenching processes of the excited states. More importantly, the exclusive photochemical reactivity of the thieno[3,2‑b]phosphole moiety of the gold(I) complex can be initiated upon photoirradiation of visible light. Stepwise photochromism of the gold(I) complex has been made possible, offering an effective strategy for the construction of multiple-state photochromic materials with multiple photocontrolled states to enhance the storage capacity of potential optical memory devices.

Photochromic Coordination Compound: Oxygen-Assisted Photoinduced Color Change for Triplet Oxygen Detection.

Detection of oxygen though color change is highly desirable for rapid qualitative analysis like the case of pH test papers. This work demonstrates 3O2-assisted photoinduced color change of a new photochromic coordination compound [Zn(4-aminopyridine)2Cl2] (ZnaPyCl), which represents the first photochromic compound with a selective 3O2 detection ability. The compound underwent photoinduced intraligand charge separation and formed a stable diradical-like triplet species in the solid state or in frozen solution, accompanied by conversion of triplet oxygen to singlet oxygen.

Polymorph acceptor-based triads with photoinduced TADF for UV sensing

In contrast to many donor–acceptor type organic luminophores exhibiting thermally activated delayed fluorescence (TADF), two deep blue TADF emitters designed in this work contain only typical electron accepting moieties with different electron accepting abilities. Derivatives of benzophenone and diphenylsulfone substituted with phenothiazine-5,5-dioxide donor moieties were synthesized and studied. In addition to the TADF, green to blue emission color switching and strong fluorescence intensity enhancement by more than 60 times was detected for THF solution of the derivative of phenothiazine-5,5-dioxide and benzophenone under increase of UV excitation dose. We proved by a variety of experimental and theoretical studies that the unusual photophysical properties of the derivative of benzophenone are mainly related to the formation of different conformers. The photostimulated intensity enhancement of the compound is due to the rise of the quantity of triplet states and their further crossing to singlet states. To our knowledge, this is the first observation of a combination of photoinduced color switching and triplet-dependent emission intensity enhancement. These properties are shown to be useful for UV sensing with very low detection limits (less than 10 μW/cm2 for the toluene solution). Under gradual increase of UV excitation dose, the DMF solution demonstrated a green → blue color swishing from (0.34; 0.44) to (0.17; 0.18) of CIE coordinates that can be detected by naked eye.

Fabrication of Anticounterfeiting Nanocomposites with Multiple Security Features via Integration of a Photoresponsive Polymer and Upconverting Nanoparticles

AbstractAnticounterfeiting materials are used to distinguish real banknotes, products, and documents from counterfeits, fakes, or unauthorized replicas. However, conventional anticounterfeiting materials generally exhibit a single anticounterfeiting function, resulting in a low level of security. Herein, a novel anticounterfeiting nanocomposite is demonstrated with numerous prominent security features. The nanocomposite is fabricated by doping upconverting nanoparticles (UCNPs) in a photoresponsive azobenzene‐containing polymer (azopolymer). Because of the cis–trans photoisomerization of the azopolymer, the nanocomposite exhibits photoinduced reversible color changes suitable for anticounterfeiting applications. Additionally, the hard nanocomposite can be converted to a rubber‐like soft solid by light irradiation. Imprinted microstructures are fabricated on the photosoftened nanocomposite, which result in photonic colors. Moreover, polarization‐dependent structures are fabricated on the nanocomposite via photoinduced orientation for encryption. Importantly, UCNPs in the nanocomposite emit visible light upon excitation by near‐infrared light, enabling the observation of various anticounterfeiting structures with high contrast. An advantage of the anticounterfeiting nanocomposite is that the security features can be observed by the naked eye for quick discrimination and can be analyzed using laboratory equipment for higher accuracy. The anticounterfeiting nanocomposite is easily processed on paper, glass, and plastic, which demonstrates its potential anticounterfeiting functions for banknotes, wines, and medicines.

Separation and Recombination of Photocarriers from Color Centers and Optically Silent Trap States from 100 to 450 K: The Halide Double Photochromic Perovskite Cs2AgBiBr6.

Compared to lead-based solar cells whose power conversion efficiency is 25.2%, the highest power conversion efficiency of a halide double Cs2AgBiBr6-based perovskite solar cell is less than 3%. It was therefore relevant to unravel the inherent reason(s) for such a low efficiency in the latter that may be related to trapping/detrapping of photocarriers. Accordingly, photocoloration and photobleaching phenomena occurring in the Cs2AgBiBr6 photochromic perovskite were examined from 100 to 450 K by diffuse reflectance spectroscopy (DRS). The separation and recombination of photogenerated charge carriers implicated both color centers and optically silent trap states within the bandgap. The processes were reversible subsequent to heating after illumination at 100 K but were mostly irreversible at 290 K. DRS spectral and kinetic measurements at T = 100-450 K were carried out after visible light illumination that further revealed the nature of the various charge carrier traps in Cs2AgBiBr6. Results confirmed the separation of photogenerated electrons and holes, with formation of the color centers identified as deep electron traps. Three different photoinduced color centers were responsible for the absorption bands observed at 1.78 (ab1), 1.39 (ab2), and 1.10 eV (ab3) at 100 K. Annealing of these electron-type color centers occurred in the temperature range of 100-450 K via recombination with holes in the valence band following their thermal release from the several hole traps. Application of a first-order kinetic model to the thermoprogrammed annealing (TPA) of the color centers' spectra yielded estimates of the activation energies of hole detrapping and lifetimes of trapped holes at room temperature. The irreversibility of photocoloration at 290 K was caused by the formation of new deep hole trap states.

Broadband Photoresponsive Bismuth Halide Hybrid Semiconductors Built with π-Stacked Photoactive Polycyclic Viologen.

Photoresponse ranges of commercially prevailing photoelectric semiconductors, typically Si and InGaAs, are far from fully covering the whole solar spectrum (∼295-2500 nm), resulting in insufficient solar energy conversion or narrow wave bands for photoelectric detection. Recent studies have shown that infinite π-aggregation of viologen radicals can provide semiconductors with a photoelectric response range covering the solar spectrum. However, controlled assembly of an infinite π-aggregate is still a great challenge in material design. Through directional self-assembly of electron-transfer photoactive polycyclic ligands, two crystalline inorganic-organic hybrid photochromic viologen-based bismuth halide semiconductors, ((Me)3pytpy)[BiCl6]·2H2O [1; (Me)3pytpy = N,N',N″-trimethyl-2,4,6-tris(4-pyridyl)pyridine] and ((Me)3pytpy)[Bi2Cl9]·H2O (2), have been synthesized. They represent the first series of pytpy-based photochromic compounds. After photoinduced coloration, the conductivities of both 1 and 2 increased. The radical products have electron absorption bands in the range of 200-1600 nm, exceeding that of Si. Both the conductivity and the photocurrent intensity of 2 are stronger than those of 1, due to better planarity, tighter π-stacking, and higher degrees of overlap of ((Me)3pytpy)3+ cations. This study not only provides a new design idea for synthesizing radical-based multispectral photoelectric semiconductors but also enriches the family of electron-transfer photochromic compounds.

High-Performance Photochromic Hydrogels for Rewritable Information Record.

Rewritable information record materials usually demand not only reversibly stimuli-responsive ability, but also strong mechanical properties. To achieve one photochromic hydrogel with super-strong mechanical strength, hydrophobic molecule spiropyran (SP) has been introduced into a copolymer based on ion-hybrid crosslink. The hydrogels exhibit both photoinduced reversible color changes and excellent mechanical properties, i.e., the tensile stress of 3.22MPa, work of tension of 12.8MJ m-3 , and modulus of elasticity of 8.6MPa. Moreover, the SP-based Ca2+ crosslinked hydrogels can be enhanced further when exposed to UV-light via ionic interaction coordination between Ca2+ , merocyanine (MC) with polar copolymer chain. In particular, hydrogels have excellent reversible conversion behavior, which can be used to realize repeatable writing of optical information. Thus, the novel design is demonstrated to support future applications in writing repeatable optical information, optical displays, information storage, artificial intelligence systems, and flexible wearable devices.

Fast T-Type Photochromism of Colloidal Cu-Doped ZnS Nanocrystals.

This paper reports on durable and nearly temperature-independent (at 298-328 K) T-type photochromism of colloidal Cu-doped ZnS nanocrystals (NCs). The color of Cu-doped ZnS NC powder changes from pale yellow to dark gray by UV light irradiation, and the color changes back to pale yellow on a time scale of several tens of seconds to minutes after stopping the light irradiation, while the decoloration reaction is accelerated to submillisecond in solutions. This decoloration reaction is much faster than those of conventional inorganic photochromic materials. The origin of the reversible photoinduced coloration is revealed to be a strong optical transition involving a delocalized surface hole which survives over a minute after escaping from intraparticle carrier recombination due to electron-hopping dissociation. ZnS NCs can be easily prepared in a water-mediated one-pot synthesis and are less toxic. Therefore, they are promising for large-scale photochromic applications such as windows and building materials in addition to conventional photochromic applications. Moreover, the present study demonstrates the importance of excited carrier dynamics and trap depths, resulting in coloration over minutes not only for photochromic nanomaterials but also for various advanced photofunctional materials, such as long persistent luminescent materials and photocatalytic nanomaterials.

AIE Ligand Constructed Zn(II) Complex with Reversible Photo-induced Color and Emission Changes

Fluoran salicylaldehyde hydrazone metal complex(FSHMC) is a kind of recently reported photo-responsive system, which has the advantages of simple synthesis, multiple colors as well as distinct color change before and after UV light irradiation. However, the emission property of FSHMC is relatively unitary. In solid state, especially, only fluorescence quench is induced after UV light irradiation, which limits their applications. In this work, a typical aggregation-induced emission(AIE) moiety of tetraphenylethene(TPE) was introduced to the design of FSHMC. The obtained FSHMC, 2-Zn, exhibited reversible color and fluorescence changes upon UV light irradiation. Due to the AIE feature of compound 2, 2-Zn exhibited different emission changes upon UV light irradiation in THF and in solid matrix, because of the fluorescence resonance energy transfer(FRET) process from TPE moiety to rhodamine B moiety.

Concomitant Photoresponsive Chiroptics and Magnetism in Metal-Organic Frameworks at Room Temperature.

Stimulus-responsive metal-organic frameworks (MOFs) can be used for designing smart materials. Herein, we report a family of rationally designed MOFs which exhibit photoresponsive chiroptical and magnetic properties at room temperature. In this design, two specific nonphotochromic ligands are selected to construct enantiomeric MOFs, {Cu2(L-mal)2(bpy)2(H2O)·3H2O}n (1) and {Cu2(D-mal)2(bpy)2(H2O)·3H2O}n (2) (mal = malate, bpy = 4, 4′ − bipyridine), which can alter their color, magnetism, and chiroptics concurrently in response to light. Upon UV or visible light irradiation, long-lived bpy− radicals are generated via photoinduced electron transfer (PET) from oxygen atoms of carboxylates and hydroxyl of malates to bpy ligands, giving rise to a 23.7% increase of magnetic susceptibility at room temperature. The participation of the chromophores (-OH and -COO−) bound with the chiral carbon during the electron transfer process results in a small dipolar transition; thus, the Cotton effects of the enantiomers are weakened along with a photoinduced color change. This work demonstrates that the simultaneous responses of chirality, optics, and magnetism can be achieved in a single compound at room temperature and may open up a new pathway for designing chiral stimuli-responsive materials.

Quantitative metabolome and transcriptome analysis reveals complex regulatory pathway underlying photoinduced fiber color formation in cotton.

As an important plant single cell model and textile application materials, poorly known about fiber color formation in cotton, which is sensitively regulated by environmental signals. Our studies underline the importance of photo signal on sensitive fiber color formation and characterize fiber color early initiation (15 DPA) and late accumulated metabolites (45 DPA) in different lighting condition. The results revealed 236 differential metabolites between control and shading, of which phenylpropanoids metabolites accounted for 20%, including uncharacterized novel metabolites and pathways. Furthermore, the early initiation specific genes respond to the absence of light are highly correlated with phenylpropanoid metabolites related to pigmentation. The current study reveals the complex pathways involving early initiation regulation and late metabolic pathways. In addition, the collection composed of uncharacterized photoinduced metabolites and early initiation signaling/regulatory genes were identified, which are important resources for understanding fiber color formation. This report provides new insight into molecular regulatory and biochemical basis underlying photoinduced fiber color formation in cotton.

Synthesis, Photophysical, Photochromic, and Photomodulated Resistive Memory Studies of Dithienylethene-Containing Copper(I) Diimine Complexes.

A series of dithienylethene-containing copper(I) diimine complexes have been synthesized and structurally characterized. Systematic studies on their photophysics, electrochemistry, and photochromism have been carried out. The photoinduced color changes of the copper(I) complexes have been achieved by photoexcitation into the metal-to-ligand charge-transfer (MLCT) absorption bands, indicating the photosensitization of light-induced cyclization by the 3MLCT excited state. In addition, by an increase in either the steric bulkiness around the copper(I) center or the structural rigidity of the complexes, the quantum efficiencies of photoluminescence and photocyclization can be effectively enhanced because of suppression of the flattening distortion of the complexes at the MLCT excited state. Furthermore, one of the complexes has been employed as an active component in the fabrication of solution-processed resistive memory devices. Notable lowering of the switching threshold voltage of the binary memory devices has been realized through photocyclization of the dithienylethene-containing copper(I) system.