A direct observation of up-converted room-temperature phosphorescence in an anti-Kasha dopant-matrix system

It is common sense that emission maxima of phosphorescence spectra (λ_P) are longer than those of fluorescence spectra (λ_F). Here we report a serendipitous finding of up-converted room-temperature phosphorescence (RTP) with λ_P < λ_F and phosphorescence lifetime > 0.1 s upon doping benzophenone-containing difluoroboron β-diketonate (BPBF₂) into phenyl benzoate matrices. The up-converted RTP is originated from BPBF₂'s T_n (n ≥ 2) states which show typical ³n-π* characters from benzophenone moieties. Detailed studies reveal that, upon intersystem crossing from BPBF₂'s S₁ states of charge transfer characters, the resultant T₁ and T_n states build T₁-to-T_n equilibrium. Because of their ³n-π* characters, the T_n states possess large phosphorescence rates that can strongly compete RTP(T₁) to directly emit RTP(T_n) which violates Kasha's rule. The direct observation of up-converted RTP provides deep understanding of triplet excited state dynamics and opens an intriguing pathway to devise visible-light-excitable deep-blue afterglow emitters, as well as stimuli-responsive afterglow materials.