Descripción del proyecto
Aromaticity, a fundamental concept in the field of chemistry, is conventionally associated with planar, conjugated two-dimensional (2D) systems. Despite its theoretical description and potential application in optoelectronic materials, 3D aromaticity induced by strong through space frontier orbital interactions remains so far little explored.
AROMASWITCH aims to exploit the complementary expertise and know-how of the host institute and the fellow to delineate the concept of Controlling Spatial Conjugation by the mechanical motion of switchable molecular tweezers. Our hypothesis is that using Ni(II)-porphyrin and/or norcorrole to place persistent, enriched π-electron at both ends of a tweezer will (a) generate three-dimensional through space conjugation in an optimized distance between two face-to-face oriented macrocycles and (b) influence the resultant (anti)aromatic character of the whole system. This approach is innovative as such through space π conjugation has not yet been explored in the molecular tweezer. We will develop macrocycles-terminated switchable molecular tweezers (i) to tweak the through space electronic conjugation in an on and off mode and (ii) to investigate the impact of 3D conjugation on aromatic property-driven photophysical and electrochemical properties. In addition, we will (iii) inspect the three-component tweezer systems in the context of the guest binding study, intercalation of aromatic or antiaromatic motifs and optoelectronics applications.
The project will thus enhance our understanding of stimuli-responsive and conformation-dependent 3D communication between (anti)aromatic rings and holds great potential for the development of smart materials with an optoelectronic response.