Deciphering the adaptive conformational evolution of dihydrophenazine derivatives in the confined space of a semi-rigid macrocyclic host

Abstract

Exploring the conformational evolution of organic molecules is a long-pursuit theme in the field of chemistry. Herein, interests are endeavored to unveil the conformational evolution of conformationally flexible dihydrophenazines with environment-sensitive and continuously-changeable fluorescence in the confined space exerted by the semi-rigid macrocyclic host ExBox4+. Co-crystals of the ExBox4+ and dihydrophenazines are obtained via vapor diffusion, facilitating direct clarification of the structural variations of the host and guests. The adaptive ground-state conformational evolution of the guests is fully deciphered via 1H NMR titration, crystallography analysis as well as systematic theoretical calculations. In contrast to the much smaller structural change of the well-noted conformationally adaptive host, the conformational variation in the central dihedral angle of the guest can be up to 22° in the crystal of the host-guest complex, which is completely different from the cases when ExBox4+ interacting with the rigid guests. Dynamic information encryption has been further achieved by harnessing the distinct fluorescence behaviors before and after host-guest complexation. This work not only provides new insights into the understanding of mutual interactions between a semi-rigid host and conformationally flexible guests, but also offers an alternative scheme for advanced information encryption based on the luminescent host-guest complexes.