Interfacial Organization Of Porphyrin, Azobenzene And Anthracene Derivatives: Supramolecular Chirality And Photoelectric, Ion Responsive Properties

Chiral supramolecular functional assemblies with great chemical structure variety and property tunability, are of crucial importance in the field of molecular recognition, asymmetric catalysis, material sciences, and especially nanotechnology and nanosciences. Chiral supramolecular functional materials play an important role in chiral subject. The properties of chiral supramolecular materials are not only determined by the molecules themselves, but also depend on the molecular packing statues. To control the function of materials by designing the building blocks at molecular level and regulating packing manners of building blocks at supramolecular level is essential and meaningful in the field of organic nanomaterials.In this dissertation, we employed porphyrin, azobenzene and anthracene derivatives as model molecules, and constructed chiral supramolecular assemblies which are controllable by interfacial organization. We discussed the effect of intermolecular interaction, molecular configuration, and packing statues of molecules on the optical and electrical properties of chiral supramolecular assemblies.Firstly, we developed a general method for constructing chiral supramolecular assemblies from achiral porphyrins, which are of guiding significance to other conjugated macrocyclic molecules, and expanded the scope of building blocks which are suitable for constructing chiral supramolecular materials through symmetry breaking at interface.Secondly, we explored the mechanism of suprmolecular chirogenesis. We used two responsive functional molecules, porphyrin and azobenzene, and controlled the supramolecular chirality of assemblies by changing counterion and photoisomerization, respectively. Our investigation confirmed that proper strength of intermolecular interaction and planar molecular configuration are essential to the formation of chiral supramolecular assemblies.The expansion of scope of building blocks and deeper insight into the mechanism of supramolecular chirogenesis provide foundation of functionalizing chiral supramolecular materials.Based on the research mentioned above, we selected an anthracene derivative and adjusted the surface pressure during the interfacial organization process to control the packing manners of building blocks and the degree of intermolecularπ-πoverlapping, and further controllably fabricated organic nanomaterials exhibiting distinct morphology, supramolecular chirality and photoswitching properties. Our research indicated that, interfacial organization of organic building blocks provided a facile way to control the morphology and photoelectric properties, and also suggested that CD spectrum can be apply not only to characterize the chirality of assemblies, but also to correlate the interactions between conjugated functional molecules.