Emissive and reactive excimers in a covalently-linked supramolecular multi-chromophoric system with a balanced...

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.