Photo-Induced Radical Generation of Supramolecular Gel with Sign-Inverted and White-Light Circularly Polarized Luminescence

The realization of persistent luminescence and in particular circularly polarized luminescence (CPL) of organic radicals remains a challenge due to their sensitivity to oxygen at ambient conditions and elusive excited state chirality control. Here, it is reported that UV-irradiation on a supramolecular gel from a chiral triarylamine derivative, TPA-Ala, led to the formation of luminescent radicals with bright CPL. TPA-Ala can form an organogel in chloroform with blue emission and supramolecular chirality as demonstrated by both CD and CPL signals. Upon UV 365 nm irradiation, an emission color change from blue to cyan is observed due to the formation of photo-induced radicals. Interestingly, it is found that the supramolecular gel radicals showed stable luminescence with a lifetime ≈ 10 days in dark environments and inverted CPL, which represents a scarce example with persistent CPL from doublet-state due to oxygen isolation ability of the gel network. Furthermore, doping a guest dye, Rhodamine B (RhB), into the supramolecular gel (RhB/TPA-Ala = 30% in molar ratio) successfully obtained a transient white-light CPL through the superposition of photo-induced radical and guest dye emissions. This work provides a useful methodology for the fabrication of radical-based CPL materials via a supramolecular assembly approach.