Stereogenic π-Conjugated Macrocycles: Synthesis, Structure, and Chiroptical Properties Including Circularly Polarized Luminescence

Highly symmetrical and aesthetically pleasing molecules have attracted the attention of organic chemists. We synthesized new highly symmetric stereogenic pi-conjugated macrocycles with planar or axial chirality. Macrocyclic oligomers synthesized by Yamamoto coupling or Suzuki-Miyaura cross-coupling from the pi-unit containing chirality. These cyclization reactions gave multiple oligomers in relatively high yields. We then elucidated their structures and investigated their chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL). Because of the selection rule for rigid and symmetric structures, these macrocycles exhibit a high dissymmetry factor (g (abs) or g (lum)) for circularly polarized light in CD or CPL. Several rigid cyclic compounds retain a highly symmetric structure in the excited state and exhibit higher g (lum) values than common chiral organic compounds. This Account provides a brief background regarding chiroptical properties, followed by a summary of the various macrocycles synthesized in this study. We are glad if this Account will be a source of ideas not only for chemists working with pi-conjugated compounds, but also for synthetic chemists working with chiral compounds, especially those engaged in asymmetric synthesis.