Molecular Triangles: A New Class of Macrocycles

Abstract

ConspectusMacrocycles have had a profound influence on the establishment of supramolecular chemistry because of their abundant molecular recognition and self-assembly characteristics. The design of new macrocyclic receptors that can be tailored by synthesis to display new and exotic properties is an important research objective for chemists and materials scientists. Rigid macrocycles with π-conjugated aromatic units, in contrast with flexible ones, tend to possess large interior and exterior π-surfaces in addition to persistent shapes. These features not only endow these macrocycles with a wide range of host-guest properties but also render them ideal building blocks for constructing a diverse variety of supramolecular architectures. The incorporation of π-conjugated units into macrocycles also imbues them with a wealth of optical, electronic, and magnetic properties, resulting in their broad application in materials science and molecular nanotechnology.Recently, we have designed and synthesized a new class of macrocycles, namely, molecular triangles, which have rigid structures with triangular geometries. They consist of three chiral trans-1,2-cyclohexano apexes and three aromatic tetracarboxylic diimide linkers, such as pyromellitic diimide, naphthalene diimide, and perylene diimide. Benefiting from the availability of facile synthetic protocols, the geometries and properties of these rigid molecular triangles can be altered at will. By combining these tetracarboxylic diimide linkers, we have been able to synthesize both molecular equilateral and isosceles triangles. During the past few years, we have conducted research in a systematic manner on the structural features and self-assembly characteristics of these molecular triangles. The following points are worthy of note regarding these molecular triangles: (i) They possess shape-persistent inner cavities of a highly electron-deficient nature. These features endow them with the ability to complex with anions and electron-rich molecules, forming supramolecular nanotubes and two-dimensional tilings. (ii) Those with intrinsic chirality are able to self-assemble into solid-state nonhelical or single-handed helical superstructures, inducing selective chirality transfer from the macrocycles to their crystalline supramolecular assemblies. (iii) The triangular arrangement of aromatic tetracarboxylic diimide linkers contributes to through-space electron delocalization encompassing the entire macrocycle, conferring exotic electronic and spin properties. To date, the family of molecular triangles has exhibited a range of physicochemical properties, such as anion recognition, chiral assembly, supramolecular gelation, energy storage, solid-state luminescence, and nonlinear optical response.In this Account, we summarize our recent progress in research into these molecular triangles. We present an overview of their design and synthesis, as well as a general summary of their structural features. Thereafter, we discuss state-of-the-art developments in relation to their molecular recognition properties and their assembly characteristics. In addition, we highlight the potential applications of these molecular triangles and their complexes with a range of solvents and electron-rich molecules. Finally, we speculate on further structural modifications and application-oriented explorations based on this class of molecular triangles.