Low-Temperature Luminescence in Organic Helicenes: Singlet versus Triplet State Circularly Polarized Emission

The experimental measurement of the photophysical and chiroptical properties of helicene-based π-conjugated emitters with electron-accepting (−CN, −py, −NO₂) or donating (TMS, NMe₂, NH₂) moieties is reported at low temperature (77 K). The samples exhibit strong circularly polarized phosphorescence in frozen solution of 2-MeTHF, with a luminescence dissymmetry factor reaching 1.6 × 10^-2 and a lifetime of over 0.46 s for the most active molecule, the nitro compound. The theoretical investigation shows that although the singlet (S₁) and triplet (T₁) excited-state emissions mainly arise from the helicene core, the rotatory strengths of the spin-allowed versus spin-forbidden emission have opposite signs. Further analysis of the spin-orbit coupling matrix elements shows that there is no strong mixing between S₁ and T₁, justifying the different signs of the rotatory strengths. In the case of the nitro compound, the enhanced phosphorescence emission is due to an efficient intersystem crossing.