Columnar Organization of Partially Fluorinated Arylene Ethynylene Macrocycles



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Porous molecular crystals have been proving themselves as an excellent emerging class of porous material not just in the solid state but also in liquid forms, as a porous liquid. They are composed of discrete molecules which hold the intrinsic pores or create extrinsic pores via weak non-covalent intermolecular interactions. Arylene ethynylene macrocycle belongs to the class porous molecular crystal, and they can be designed to be shape persistent as well as of different shape, sizes, and functionalities. In addition, these macrocyclic compounds self-aggregate via [π···π] interaction to form higher ordered material. This dissertation presents the syntheses of partially fluorinated arylene ethynylene macrocycles and their crystallographic study to understand the influence of fluoroarene rings on their self-aggregation properties. Chapter 1 introduces porous molecular crystal and their emerging development into porous liquids, as well as the arylene ethynylene macrocycle and their self-aggregation and liquid crystalline properties. Chapter 2 includes the synthesis of diamond-shaped partially fluorinated macrocycles with alternating arene and fluoroarene bridged by ethynylene units. This chapter presents the role of π-interactions between the fluoroarene and the alkyne moieties to direct the columnar organization of the macrocycles. Chapter 3 presents the designed pentagonally and hexagonally partially fluorinated macrocycles and their crystallographic studies to understand the intermolecular interactions leading to the formation of higher ordered material. Chapter 4 presents the idea and design of the partially fluorinated arylene ethynylene macrocyclic compound to create porous liquid crystals.





Portions of this document appear in: Karki, Sumitra, Lucas J. Karas, Xiqu Wang, Judy I. Wu, and Ognjen Š Miljanić. "Synthesis and Columnar Organization of Partially Fluorinated Dehydrobenz [18] annulenes." Crystal Growth & Design 22, no. 4 (2022): 2076-2081.