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Phosphorescence is a process that slowly releases the photoexcitation energy after the removal of the excitation source. Although transition metal complexes and purely organic room-temperature phosphorescence (RTP) materials show excellent phosphorescence property, their applications in in vitroand in vivobioimaging are limited due to their poor solubility in water. To overcome this issue, phosphorescent materials are modified with amphiphilic or hydrophilic polymers to endow them with biocompatibility. This review focuses on recent advances in the development of phosphorescent probes for in vitroand in vivobioimaging. The photophysical mechanism and the design principles of transition metal complexes and purely organic RTP materials for the stabilization of the triplet excited state for enhanced phosphorescence are first discussed. Then, the applications in in vitroand in vivobioimaging using transition metal complexes including iridium(iii) complexes, platinum(ii) complexes, rhodium(i) complexes, and purely organic RTP materials are summarized. Finally, the current challenges and perspectives for these emerging materials in bioimaging are discussed.

Herein, a complex micelle as an oxygen nano-carrier is constructed through the hierarchical assembly of the diblock copolymer poly(ethylene glycol)-block-poly(l-lysine) (PEG-b-PLys), tetrakis(4-sulfonatophenyl)porphinato cobalt(ii) (Co(ii)TPPS), a heptapeptide (Cys-His-His-His-His-His-His) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD). Co(ii)TPPS was encapsulated into the cavities of TM-β-CDs driven by the host–guest interaction so that the irreversible formation of a μ-oxo-dimer of Co(ii)TPPS can be effectively prevented. The imidazole groups of the heptapeptide were selected as good axial ligands coordinating to the centric cobalt of Co(ii)TPPS, which subtly constituted the five-coordinated precursor serving as an active functional centre for oxygen binding. The sixth position of Co(ii)TPPS can bind oxygen. Furthermore, the host–guest inclusion (TM-β-CD/Co(ii)TPPS) was loaded into the hydrophobic core of the complex micelle and tightly fixed with PLys chains. The hydrophilic PEG blocks stretched in the aqueous solution constitute the shells which stabilize the structure of the complex micelle as well as impart the complex micelle sufficient blood circulation time. Moreover, the complex micelle exhibited excellent biocompatibility and cellular uptake. Therefore, the rationally designed amphiphilic structure can work as promising artificial O2carriers in vivo. Potentially, the complex micelle can be expected to change the anaerobic microenvironment and find applications in the repair of the cells damaged by cellular hypoxia.