Dithia[9]helicenes: Molecular design, surface imaging, and circularly polarized luminescence with enhanced dissymmetry factors

Abstract

Synthesis of two dithia[9]helicenes by means of a LED-based double photocyclization is reported. The compounds have sulfur atoms placed at the terminal rings of the helicene, and they display two alternative C₂-symmetrical arrangements named exo (1) and endo (2). Separation of enantiomers of opposite helicity allowed the complete characterization in solution, in silico, by X-ray crystallography, and adsorbed on gold. The theoretical analysis confirms the unexpected finding that endo-dithia[9]helicene displays an experimental dissymmetry factor (g_lum) in CPL larger than its isomer exo-dithia[9]helicene (–0.0125 vs. −0.0042). This enhanced g_lum factor ranks among the largest for a helicene-type molecule. Comparison with smaller analogues, namely exo and endo-dithia[7]helicenes (10 and 11, respectively), is also presented.