Chiral Benzo[b]silole-Fused 9,9'-Spirobi[fluorene]: Synthesis, Chiroptical Properties, and Transformation to π-Extended Polycyclic Arene.

Chiral spiro π-conjugated compounds have emerged as a new class of circularly polarized luminescent organic materials. Here we report the synthesis and (chir)optical properties of a chiral benzo[b]silole-fused 9,9'-spirobi[fluorene] (SBF) and π-extended spiro polycyclic arene. The benzo[b]silole-fused SBF was successfully synthesized by a rhodium-catalyzed intramolecular silylative cyclization. It was further transformed to the chiral π-extended spiro polycyclic arene by an annulative π-extension reaction. Less effective spiroconjugation was observed for these spiro compounds through UV-Vis absorption spectroscopy and theoretical calculations. They exhibit circularly polarized luminescence with the dissymmetry factors of up to 0.76×10-3 . Theoretical calculations demonstrate that emission of the benzo[b]silole-fused SBF occurs from one subunit, the structure of which is slightly different from that in the Frank-Condon state.