Bright, persistent, room-temperature phosphorescence (RTP) at long wavelengths is crucial for high-resolution imaging in the absence of in vivo autofluorescence. However, efficient long-wavelength RTP is difficult. Here, enhanced red RTP based on a unique mechanism was observed from deuterated dibenzo[g.p]chrysenes substituted with a phenoxazine. The yield was 16%, with an average lifetime of 1.8 s. An orthogonal dihedral angle between the dibenzo[g.p]chrysene and the phenoxazine in the lowest excited singlet state allowed a forbidden fluorescence to increase triplet generation. When the dihedral angle changed, disengagement of the forbidden fluorescence from the excited singlet state occurred, and the lowest triplet excited state had a facilitated phosphorescence rate without increasing its nonradiative transition rate. The facilitated phosphorescence rate as well as the large triplet yield led to the enhanced red RTP.
Förster-resonance energy transfer (FRET T-S ) from the lowest excited triplet state (T 1 ) of a donating sensitizer to a fluorescence acceptor can be used to obtain bright room-temperature afterglow emission at long wavelengths. However, the energy transfer from the lowest excited singlet state of the donor to the acceptor is an undesirable deactivation pathway that prevents FRET T-S . Herein, heteroatoms in chromophores are shown to allow selective and efficient FRET T-S for enhanced triplet emission for bright roomtemperature afterglow emission at long wavelengths. Different transition characteristics between the lowest singlet excited state and triplet states in heteroatom-containing chromophores accelerate triplet generation, enabling near-zero fluorescence yields. Out-of-plane vibrations of the heteroatoms in aromatic fused rings greatly enhance the radiative rate from T 1 by a factor of 88 relative to non-heteroatom-containing fused chromophore. The compatibility of the near-zero fluorescence and the enhanced triplet emission in a heteroatom-containing fused chromophore enable selective and efficient FRET T-S pathways, resulting in room-temperature red afterglow emission with a yield of 17%. The bright emission at long-wavelengths allows distinguishable, multiple spectral signals in ambient white light.
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