Emissive and reactive excimers in a covalently-linked supramolecular multi-chromophoric system with a balanced rigid-flexible structureстатья
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Дата последнего поиска статьи во внешних источниках: 8 апреля 2022 г.
Аннотация:A novel multi-chromophoric system, triad, in which two styrylbenzoquinoline (SBQ) photochromes are connected by a balanced rigid-flexible linker comprising 2,3-naphthylene framework (a residue of 3-oxy-2-naphthoic acid) and tetramethylene groups, was designed and synthesized to study an excimer formation in the excited state. The 1H NMR data testified that triad exists in solution as folded conformers with asymmetric parallel-displaced SBQ units. Under light irradiation, in the triad, competitive photoisomerization and [2 + 2] photocycloaddition reactions were observed, both reactions being reversible. The photocycloaddition resulted in a tetrasubstituted cyclobutane. The red-shifted fluorescence spectrum and the appearance of a long-lived component in the triad fluorescence decay indicated formation of an 'emissive' excimer. The photocycloaddition is assumed to occur in a 'reactive' excimer, in which the ethylene groups of the SBQ photochromes are located at a distance sufficient for the formation of the σ-bonds between them. Quantum-chemical density functional theory (DFT) calculations at M06-2X/6-31G* level predicted the existence of the triad conformers with π-stacking interaction of SBQ photochromes, the structure of which is pre-organized for the excimer formation and photocycloaddition. For the first time, both emissive and reactive excimers were experimentally observed in the multi-chromophoric system with two diarylethylene photochromes undergoing [2 + 2] photocycloaddition.