Multi‐Helical Architectures and Heteroatom Doping: Design Strategies for Enhancing Photophysical Performance in Helicene‐Based Materials

Abstract Background: Multiple [ n ]helicenes, characterized by their intense light absorption, inherent chirality, and circularly polarized luminescence (CPL), have emerged as pivotal candidates for advancing (chiral) optical materials and next generation optoelectronic devices. Current Status: Recent progress in helicene materials has intensified interest in their unique multihelical architectures, the incorporation of heteroatoms, and the achievement of outstanding photoluminescent performances. However, systematic insights into how structural variations in multiple [ n ]helicenes govern their photophysical behavior remain scarce. Content of this Review: This review provides a comprehensive discussion on how structural design factors, including core types, heteroatom doping, multihelical configurations/conformations, π‐system expansion, and backbone rigidity, influence molecular light absorption, and key photoluminescent properties, such as UV–vis absorption, circular dichroism, fluorescence emission, photoluminescence quantum yield ( Φ PL ), and CPL performance. Significance: A deeper understanding of the relationship between structure and photophysical performance in multiple [ n ]helicenes is essential for guiding the design and development of high performance chiral optical materials.