π-Stacking Conversion and Enhanced Force-Stimuli Response of a Divinylanthracene Derivative in a Hydrogen-Bonded Framework

Abstract

Hydrogen bond-induced π-stacking conversion was used to achieve an enhanced force-stimuli response of 9,10-bis(2-(pyridin-4-yl)vinyl)anthracene (BP4VA). In BP4VA crystals, the molecules adopted a J-aggregate pattern, and no overlap between the central anthracene planes was observed. Trimesic acid (TA) as a hydrogen bond donor could promote the transformation of the π-stacking type of BP4VA as a hydrogen bond acceptor. It was found that TA and BP4VA molecules formed two-dimensional lamellar hydrogen-bonded frameworks with large windows, which were filled by BP4VA molecules belonging to other layers. Within such three-dimensional packing, J-aggregate stacking type of BP4VA converted into a mixture of J-type and H-type dimers. Moreover, BP4VA adopted a highly twisted conformation, and π–π interaction between them was very weak. So, the hydrogen-bonded complex emitted a short wavelength fluorescence. More importantly, the yellow hydrogen-bonded complex turned into red solids under force stimuli, and its fluorescence had a fairly large shift of more than 110 nm. This is in contrast with a spectral shift of 43 nm from the sheared neat BP4VA crystals. Quantum chemical calculation and spectral observations implied that the planarization, shortened π-distance, and large overlap between anthracence units should be responsible for the large spectral shift. The results imply that the appropriate acid as a hydrogen bond donor might help distyrylanthracene derivatives possess outstanding functions.