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Formation of Functional Cyclooctadiene Derivatives by Supramolecularly-Controlled Topochemical Reactions and Their Use as Highly Selective Fluorescent Biomolecule Probes
摘要： Controlling the regio- and stereochemistry of the photoproducts in solution is far more challenging for polyenes than for monoalkenes. Herein, a supramolecularly-controlled topochemical reaction of conjugated dienes in homogeneous system is developed, ultimately providing two cyclooctadiene-cored tetraimidazolium molecular receptors exclusively. These cyclooctadiene derivatives exhibited highly sensitive and selective fluorescence sensing for thymine relative to other biologically relevant species in aqueous solution at physiological pH. Both the cyclooctadiene moieties and imidazolium units play important roles in the selective recognition observed. The presented supramolecularly-controlled method allows the simple yet rare selective photoconversion of flexible cyclooctadiene derivatives in solution. This study offers a new synthetic strategy for the preparation of functional molecules with potential for use in biological applications.
关键词： thymine recognition,fluorescent biomolecule probes,supramolecularly-controlled topochemical reaction,cyclooctadiene derivatives
更新于2025-09-23 15:19:57
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Regio- and stereo-selective [4+4] photodimerization of angular-shaped dialkyltetracenedithiophene
摘要： Angular-shaped dialkyltetracenedithiophenes (aTDTs) undergo [4+4] photodimerization in solution to form a butterfly-shaped skeleton. This reaction proceeds in a regio- and stereo-selective manner, forming only a single planosymmetric syn-[2,2]-daTDT out of six possible products. The photocycloaddition of aTDTs can take place topochemically in the thin-film state while maintaining regio- and stereo-selectivity. Stronger aliphatic dispersion forces and π–π interactions play important roles in forming the eclipsed dimeric complex that leads to the syn-[2,2]-daTDT isomer.
关键词： regio-selectivity,tetracenedithiophene,stereo-selectivity,topochemical reaction,photodimerization
更新于2025-09-19 17:15:36
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Silicene Quantum Dots Confined in Few-Layer Siloxene Nanosheets for Blue Light-Emitting Diodes
摘要： Two-dimensional silicon-based materials have unique physical and chemical properties due to high surface area and quantum confinement effects. Herein, a topochemical reaction method is used for preparing silicene quantum dots confined in few layer siloxene nanosheets with FeCl3?6H2O as oxidant, which shows thickness less than 2 nm. The experimentally prepared siloxene nanosheets are dispersible, with silicene quantum dots having average diameter less than 5 nm. The silicene quantum dots are self-organized through the oxidation of FeCl3, showing unique optical properties of blue emission. The UV-visible absorption and PL emission spectra indicate the quasi-direct band gap transition to the emission. Besides, the few-layer siloxene nanosheets with silicene quantum dots have a radiative lifetime of 1.098 ns at an emission wavelength of 435 nm, which derives from the quasi-direct band transition of silicene quantum dots. Such two-dimensional nanosheets of silicon possess potential applications for the emitting layer materials of blue light-emitting diodes (LED).
关键词： topochemical reaction,silicene quantum dot,photoluminescence,siloxene,quasi-direct band gap
更新于2025-09-12 10:27:22