Triarylborane-Based Helical Donor-Acceptor Compounds: Synthesis, Photophysical, and Electronic Properties.

We report herein the synthesis and characterization of 10-(dimesitylboryl)-N,N-di-p-tolylbenzo[c]phenanthren-4-amine (3-B(Mes)2-[4]helix-9-N(p-Tol)2 1) and 13-(dimesitylboryl)-N,N-di-p-tolyldibenzo[c,g]phenanthren-8-amine (3-B(Mes)2-[5]helix-12-N(p-Tol)2 2). Their electrochemical and photophysical properties have been studied experimentally and theoretically. The donor and acceptor substituted helicene derivatives exhibit moderate fluorescence quantum yields in THF (Φf = 0.48 and 0.61 for 1 and 2, respectively), which are higher than unsubstituted ones (Φf = 0.18 for [4]helicene; Φf < 0.05 for [n]helicenes (n ≥ 5)). In the solid state, the Φf values are higher (Φf = 1.00 and 0.55 for 1 and 2, respectively) than those in solution, most likely due to the restrictions of molecular motions. The S0 → S1 transitions of 1 and 2 are predominately HOMO → LUMO transitions. Upon excitation with UV light, the interplanar angle between the two terminal aryl rings of the [5]helix core of 2 decreases (S1 state compared with S0 state), which is similar to placing a spring under an external force.