Chiroptical Properties of Chiral Macrocycles Composed of Axially Chiral Binaphthyl and Bithiophene

Stereogenic macrocycles composed of axially chiral binaphthyls and bithiophenes were synthesized. The bis(1,5‐cyclooctadiene)nickel(0)‐catalyzed coupling of an enantiomeric precursor yielded a cyclic dimer and trimer with doubly‐twisted and triply‐twisted triangular geometries, respectively. The orientation of the bithiophenes, s‐cis, and s‐trans in the cyclic compounds significantly altered their macrocyclic structure. Mixing of conformers in the cyclic dimer results in complex chiroptical properties, leading to bisignate‐type spectra, which are rarely observed in circularly polarized luminescence.