Photochromic [2]rotaxanes with bidirectional photoswitchability were fabricated, whose colored states exhibit remarkable visible-light and thermal stabilities as revealed by systematically spectroscopic investigations.
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http://dx.doi.org/10.1039/c8cc05294h | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter, The State Key Laboratory of Structural Chemistry, 155 Yangqiao Road West, 350002, Fuzhou, CHINA.
Macrocycles represent one important class of functional molecules, and dynamic macrocycles with the potential of cleavability, adaptability, and topological conversion are challenging. Herein we report photoswitchable allosteric and topological control of dynamic covalent macrocycles and further the use in guest binding and mechanically interlocked molecules. The manipulation of competing ring-chain equilibria and bond formation/scission within reaction systems enabled light-induced structural regulation over dithioacetal and thioacetal dynamic bonds, accordingly realizing bidirectional switching between crown ether-like covalent macrocycles and their linear counterparts.
View Article and Find Full Text PDFNat Commun
October 2024
Laboratory of Biomolecular Research, PSI Center for Life Sciences, Villigen-PSI, Switzerland.
Opsins are G protein-coupled receptors (GPCRs) that have evolved to detect light stimuli and initiate intracellular signaling cascades. Their role as signal transducers is critical to light perception across the animal kingdom. Opsins covalently bind to the chromophore 11-cis retinal, which isomerizes to the all-trans isomer upon photon absorption, causing conformational changes that result in receptor activation.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai 200240, China.
Azo molecules, being extensively studied as photoswitches, have demonstrated versatile photoswitching performance and applications in solution-phase systems. However, the dense molecular packing and insufficient conformational freedom in the solid/crystalline state typically pose a challenge to their ⇆ isomerization. This study presents a breakthrough in solid-state azo chemistry, where the investigated azobispyrazole molecules are capable of achieving high → photoconversion, ranging from 85% to nearly quantitative (96%), and quantitative → photoswitching in their crystalline states.
View Article and Find Full Text PDFChem Commun (Camb)
September 2024
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
We present a facile and ultrafast mechanosynthesis of hydrogen-bonded organic frameworks |CNH‖HCO| with UV and NIR bidirectional photoswitching of photochromic/photothermal behavior. The reaction time is reduced to mere seconds, and the method is both high-yield and scalable.
View Article and Find Full Text PDFChemistry
August 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Sector 81, SAS Nagar, Knowledge City, 140 306, Manauli, Punjab, India.
We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated.
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