Photophysics and photochemistry of thermally activated delayed fluorescence emitters based on the multiple resonance effect: transient optical and electron paramagnetic resonance studies

The photochemistry of two representative thermally activated delayed fluorescence (TADF) emitters based on the multiple resonance effect (MRE) ( DABNA-1 and DtBuCzB ) was studied. No significant TADF was observed in fluid solution, although the compounds have a long-lived triplet state ( ca. 30 μs). We found that these planar boron molecules bind with Lewis bases, e.g. , 4-dimethylaminopyridine ( DMAP ) or an N -heterocyclic carbene ( NHC ). A new blue-shifted absorption band centered at 368 nm was observed for DtBuCzB upon formation of the adduct; however, the fluorescence of the adduct is the same as that of the free DtBuCzB . We propose that photo-dissociation occurs for the DtBuCzB-DMAP adduct, which is confirmed by femtosecond transient absorption spectra, implying that fluorescence originates from DtBuCzB produced by photo-dissociation; the subsequent in situ re-binding was observed with nanosecdon transient absorption spectroscopy. No photo-dissociation was observed for the NHC adduct. Time-resolved electron paramagnetic resonance (TREPR) spectra show that the triplet states of DABNA-1 and DtBuCzB have similar zero field splitting (ZFS) parameters ( D = 1450 MHz). Theoretical studies show that the slow ISC is due to small SOC and weak Herzberg-Teller coupling, although the S 1 /T 1 energy gap is small (0.14 eV), which rationalizes the lack of TADF. The photophysics of thermally activated delayed fluorescence emitters based on the multiple resonance effect was studied.