Mn(iii)-mediated C–P bond activation of diphosphines: toward a highly emissive phosphahelicene cation scaffold and modulated circularly polarized luminescence

Transition metal mediated C–X (X = H, halogen) bond activation provides an impressive protocol for building polyaromatic hydrocarbons (PAHs) in C–C bond coupling and annulation; however, mimicking both the reaction model and Lewis acid mediator simultaneously in a hetero-PAH system for selective C–P bond cleavage faces unsolved challenges. At present, developing the C–P bond activation protocol of the phosphonic backbone using noble-metal complexes is a predominant passway for the construction of phosphine catalysts and P-center redox-dependent photoelectric semiconductors, but non-noble metal triggered methods are still elusive. Herein, we report Mn(iii)-mediated C–P bond activation and intramolecular cyclization of diphosphines by a redox-directed radical phosphonium process, generating phosphahelicene cations or phosphoniums with nice regioselectivity and substrate universality under mild conditions. Experiments and theoretical calculations revealed the existence of the unusual radical mechanism and electron-deficient character of novel phosphahelicenes. These rigid quaternary bonding skeletons facilitated versatile fluorescence with good tunability and excellent efficiency. Moreover, the enantiomerically enriched crystals of phosphahelicenes emitted intense circularly polarized luminescence (CPL). Notably, the modulated CPL of racemic phosphahelicenes was induced by chiral transmission in the cholesteric mesophase, showing ultrahigh asymmetry factors of CPL (+0.51, −0.48). Our findings provide a new approach for the design of emissive phosphahelicenes towards chiral emitters and synthesized precursors.