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Photochromic compounds are well-known for their promising applications in many areas. In this context, many different photochromic families have been developed. As the early study of these photochromic compounds was mainly focused on the organic system, their photochromic reactivity was mainly derived from the singlet excited state. We hypothesized that the incorporation of the photochromic ligand to the transition metal complex and coordination complex systems would not only render the triplet state of the organic photochromic system more readily accessible due to the large spin-orbit coupling of the heavy metal center but also would lead to ready extension of the excitation wavelength to less destructive longer wavelength low-energy excitation. On the other hand, the long-lived triplet excited states of the metal complexes are also suitable for energy or electron transfer processes, which should lead to new photochromic behavior and photoswitchable functional properties. Through the incorporation of the stilbene-, azo-, spirooxazine-, and dithienylethene-containing ligands to transition metal complex systems with heavy metal centers and suitable excited states, triplet state photosensitized photochromism has been achieved. With the triplet state photosensitization, the photochromism of these compounds could be extended from the high energy UV region to the visible region. In the development of dithienylethene-containing ligands, we have adopted an alternative strategy, which involves the incorporation of nitrogen and sulfur heterocycles that directly form part of the dithienylethene framework as ligands to exert a much stronger perturbation and influence on the excited state properties of the photochromic unit by the metal center. On the basis of the new design, wide ranges of dithienylethene-containing ligands, including phenanthrolines, 2-pyridylimidazoles, N-pyridylimidazol-2-ylidenes, cyclometalating thienylpyridines, β-diketonates, and β-ketoiminates have been designed and incorporated into various coordination systems. Apart from the photosensitization, tuning of the closed form absorption and photochromic behavior based on the perturbation of the metal center, coordination-assisted planarization, modification of the ancillary ligands and introduction of various electronic excited states derived from the coordination system have been successfully demonstrated. This strategy can be used for developing NIR photochromic dithienylethenes. With the above effects observed upon the coordination to different transition metal centers and central atoms, this strategy offers a simple and effective way for the modification of the photochromic characteristics. Moreover, the emission and other functional properties of the coordination systems could also be photoswitched by the photochromic reactions.
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http://dx.doi.org/10.1021/acs.accounts.7b00426 | DOI Listing |
Adv Sci (Weinh)
December 2024
College of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, 650093, China.
This study presents a multi-mode X-ray detection and imaging strategy by integrating photochromism, photoluminescence, and radioluminescence into Tb-doped CaAlSiO. CaAlSiO: Tb exhibits stable radioluminescence, oxygen vacancy-related photochromism, and photoluminescence modulation, all of which showed a linear relationship with X-ray exposure. This multi-mode response enables high-quality imaging and detection in both bright and dark conditions, facilitating time-dependent cumulative X-ray radiation dose assessments.
View Article and Find Full Text PDFNanoscale
December 2024
School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, USA.
Molybdenum disulfide (MoS) is a notable two-dimensional (2D) transition metal dichalcogenide (TMD) with properties ideal for nanoelectronic and optoelectronic applications. With growing interest in the material, it is critical to understand its layer-number-dependent properties and develop strategies for controlling them. Here, we demonstrate a photo-modulation of MoS flakes and elucidate layer-number-dependent charge transfer behaviors.
View Article and Find Full Text PDFRSC Adv
December 2024
Department of Chemistry, Faculty of Science, Tokyo University of Science 1-3 Kagurazaka Shinjyuku-ku Tokyo 162-8601 Japan
A novel photochromic system was discovered, in which leucomethylene blue, reduced by l-ascorbic acid, was irradiated with 405 nm visible light, resulting in the solution undergoing a colorless-to-blue transition. The process was then repeated, with the solution returning to its colorless state when left undisturbed. This photochromic reaction is sensitive enough to be driven by a blue-violet LED lamp and enables figures to be drawn in solution with a laser pointer.
View Article and Find Full Text PDFSmall
December 2024
Department of Polymer-Nano Science and Technology, Department of Nano Convergence Engineering, Jeonbuk National University, Jeonju, 54896, Republic of Korea.
A diarylethene-based zwitterionic molecule (DZM) is newly synthesized for the development of smart films exhibiting reversible color change and switchable ionic conductivity in response to external light stimuli. This dual molecular building block is constructed through zwitterionic interlocking and strong phase separation between the dendron-shaped aliphatic tails and the diarylethene head. Uniaxial shear coating and molecular self-assembly result in anisotropically oriented nanostructures, which are further solidified through photopolymerization.
View Article and Find Full Text PDFAdv Mater
December 2024
Nanotechnology Center, School of Fashion and Textiles, The Hong Kong Polytechnic University Hung Hom, Kowloon, Hong Kong, 999077, China.
Smart wearable devices with dynamically reversible color displays are crucial for the next generation of smart textiles, and promising for bio-robots, adaptive camouflage, and visual health monitoring. The rapid advancement of technology brings out different categories that feature fundamentally different color-reversing mechanisms, including thermochromic, mechanochromic, electrochromic, and photochromic smart wearables. Although some reviews have showcased relevant developments from unique perspectives, reviews focusing on the advanced design of flexible chromic wearable devices within each category have not been reported.
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