Chiroptical properties of symmetric double, triple, and multiple helicenes

Abstract

Helicenes have attracted considerable attention due to their inherent helical chirality and extended π-conjugation. Recently, rapid progress has been witnessed in the preparation of double, triple, quadruple, quintuple, and sextuple helicenes, where plural helicene moieties are symmetrically arranged in a single molecule. While synthetic efforts and X-ray crystallographic analyses devoted to these multiple helicenes and theoretical investigations on their isomerization and racemization behaviors have been relatively well documented and reviewed in the literature, the chiroptical properties of the multiple helicities have been somewhat overlooked. This review discourses the cumulative and systematic investigations on the chiroptical properties such as the circular dichroism (CD) and circularly polarized luminescence (CPL) of multiple helicenes. Although the number and structural variations of multiple helicenes reported to date have been fairly limited, this review overviews the current status of the chemistry of multiple helicenes from the viewpoint of chiroptical properties and provides insights into the design principle for advanced chiroptical materials through the proper arrangement of multiple helices, highlighting the impact of the molecular symmetry on the chiroptical responses.