Circularly polarized luminescence of inherently chiral macrocycles

Inherently Chiral Macrocycles (ICMs) exhibit significant potential in the field of chiral photofunctional materials due to their unique form of chirality presentation, molecular rigidity, and tunable cavity structures. However, constrained by the synthetic challenges of obtaining ICMs with high enantiomeric purity, their circularly polarized luminescence (CPL) properties have not been systematically investigated. In recent years, our group has developed a variety of efficient catalytic asymmetric synthesis strategies, successfully constructing a series of structurally diverse inherently chiral calixarenes, heteracalixarenes, beltarenes, and their derivatives, and has conducted in-depth exploration of their CPL performance. Research indicates that by rationally modulating molecular symmetry, enhancing molecular rigidity, extending the π-conjugated skeleton, and introducing functionalized substituents, the luminescence dissymmetry factor (glum) can be significantly enhanced, reaching up to 2.2×10−2. Furthermore, dynamic modulation of CPL signals can also be achieved through pH regulation and host-guest interactions. This article systematically reviews the aforementioned research findings, focusing on elucidating the intrinsic relationship between the structural characteristics of inherently chiral macrocyclic molecules and their CPL properties, aiming to provide new insights and molecular platforms for the future development of high-performance CPL materials.