Comprehensive Summary
Organic room‐temperature phosphorescence (RTP) materials have attracted immense attention in bioimaging due to their long emission lifetime and large Stokes shift. RTP materials with long emission wavelength can improve the penetration depth for bioimaging. However, the design of red persistent RTP materials is still challenging. In this study, a fused‐ring structure has been proposed to effectively decrease the triplet energy level, thus extending the emission wavelength of phosphorescence. In addition, the fused‐ring structure exhibits a high molar extinction coefficient (ɛ) and high luminescence efficiency due to the rigid structure. A new class of crystalline hosts (iminodibenzyl, IDB) are developed to stabilize the triplet excitons that are generated from the fused‐ring molecules. The maximum RTP wavelength of doping materials can reach 635 nm with a lifetime of 9.35 ms. Water‐disperse nanoparticles are successfully prepared for in vivo time‐resolved bioimaging, which eliminates the background fluorescence interference from biological tissues. These reveal a delicate design strategy for the construction of long‐wavelength emissive RTP materials for high‐resolution bioimaging.