Molecular photoswitch research has drawn much attention in the last century owing to its great potential in the development of smart materials. However, photoswitches suitable for constructing light-responsive luminescent materials remain limited, especially those involving triplet-state phosphorescence. Herein, we designed a novel molecular photoswitch based on the conformation transition of phenothiazine derivatives, minimizing steric hindrance (-CH > -Cl > -F) to regulate the conformation transition process while introducing a cyanobenzene acceptor to promote phosphorescence emission potential. When they were doped into a polymer matrix, varying photoswitch rates were achieved by incorporating different steric hindrance groups into phenothiazine or cyanobenzene groups, accompanied by photoresponsive room-temperature phosphorescence. This study is expected to greatly expand the diversity and applications of organic photoswitch molecules.
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http://dx.doi.org/10.1021/jacs.4c14920 | DOI Listing |
Macromol Rapid Commun
January 2025
Wuhan National Laboratory for Optoelectronics, School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, China.
Hexaarylbiimidazole (HABI) molecules have awakened a broad interest in photo-processing, super-resolution imaging, photoinduced self-healing materials, and photomechanical hydrogels due to their excellent photosensitivity and photo-induced cleavage properties. In this work, a novel photoswitchable branched polyurethanes (BPU), which are synthesized by copolymerizing HABI with glycerol, isophorone diisocyanate (IPDI), and polyethylene glycol (PEG), is designed. 7-Diethylamino-4-methylcoumarin (DMCO) is introduced as a radical quencher, which can not only avoid the hydroxyl interfering from conventional radical scavengers during the polymerization process but also promote efficient quenching of TPIR radicals.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK.
The ground and excited state electronic structure of the molecular photoswitches quadricyclane and norbornadiene is examined qualitatively and quantitatively. A new custom basis set is introduced, optimised for efficient yet accurate calculations. A number of advanced multi-configurational and multi-reference electronic structure methods are evaluated, identifying those sufficiently accurate and efficient to be used in on-the-fly simulations of photoexcited dynamics.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology 5600 MB Eindhoven The Netherlands
Using photoswitchable molecules to manipulate supramolecular interactions under light illumination has driven advancements in numerous fields, allowing for the strategic alteration of molecular systems. However, integrating the moiety responsible for these interactions into the photochromic scaffold can be complex and may hamper the switching efficiency. We thus explored a simple class of organic molecules, namely thiosemicarbazones, featuring both a photoisomerizable C[double bond, length as m-dash]N double bond and a thiourea moiety capable of hydrogen bonding.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Laboratory of Advanced Computation and Theory for Materials and Chemistry, Department of Chemistry, National Institute of Technology Warangal (NITW), Warangal, Telangana-506004, India.
The optical control of physiological processes with high precision using photoswitches is an emerging strategy for non-invasive diagnosis and therapies, providing innovative solutions to complex biomedical challenges. Light-responsive cyclic conjugated-dienes (cCDs) have long been recognized for their 4π-photocyclization; however, photoswitching behaviour in medium-sized cCDs has recently been reported, representing a pioneering discovery in the field. Reinforced by previous experimental evidence corroborating the Woodward-Hoffmann rules, this report provides insight into the origin of the exotic dual photoexcitation mechanism devised to achieve thermo-reversible photoswitching in large cCDs with cyclodeca-1,3-diene as a prototype.
View Article and Find Full Text PDFChemistry
January 2025
SciLifeLab, Department of Chemistry, Umeå University, 90187, Umeå, Sweden.
Chemically induced dimerization/proximity (CID/CIP) systems controlled by chemical dimerizers (also known as molecular glues) provide valuable means for understanding and manipulating complex, dynamic biological systems. In this study, we present the development of versatile chemo-optogenetic systems utilizing azobenzene-based photoswitchable molecular glues (sMGs) for reversible protein dimerization controlled by visible light. These systems allow multiple cycles of light-induced dimerization, overcoming the limitations of irreversible photolysis in previous systems.
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