Exploiting racemism enhanced organic room-temperature phosphorescence to demonstrate Wallach's rule in the lighting chiral chromophores.

The correlation between molecular packing structure and its room-temperature phosphorescence (RTP), hence rational promotion of the intensity, remains unclear. We herein present racemism enhanced RTP chiral chromophores by 2,2-bis-(diphenylphosphino)-1,1-napthalene (rac-BINAP) in comparison to its chiral counterparts. The result shows that rac-BINAP in crystal with denser density, consistent with a long standing Wallach’s rule, exhibits deeper red RTP at 680 nm than that of the chiral counterparts. The cross packing between alternative R- and S- forms in rac-BINAP crystal significantly retards the bimolecular quenching pathway, triplet-triplet annihilation (TTA), and hence suppresses the non-radiative pathway, boosting the RTP intensity. The result extends the Wallach’s rule to the fundamental difference in chiral-photophysics. In electroluminescence, rac-BINAP exhibits more balanced fluorescence versus phosphorescence intensity by comparison with that of photoluminescence, rendering a white-light emission. The result paves an avenue en route for white-light organic light emitting diodes via full exploitation of intrinsic fluorescence and phosphorescence. Room temperature phosphorescence (RTP) is a topic which is currently widely studied, but a study on the correlation between types of molecular solid and RTP properties is lacking. Here the authors show that RTP is enhanced in the racemic form of axial chiral molecules due to its denser R- and S- cross packing arrangement.