Ultralong organic phosphorescence (UOP) based on metal-free porous materials is rarely reported owing to rapid nonradiative transition under ambient conditions. In this study, hydrogen-bonded organic aromatic frameworks (HOAFs) with different pore sizes were constructed through strong intralayer π-π interactions to enable ultralong phosphorescence in metal-free porous materials under ambient conditions for the first time. Impressively, yellow UOP with a lifetime of 79.8 ms observed for PhTCz-1 lasted for several seconds upon ceasing the excitation. For PhTCz-2 and PhTCz-3, on account of oxygen-dependent phosphorescence quenching, UOP could only be visualized in N2 , thus demonstrating the potential of phosphorescent porous materials for oxygen sensing. This result not only outlines a principle for the design of new HOFs with high thermal stability, but also expands the scope of metal-free luminescent materials with the property of UOP.
Keywords: hydrogen bonds; hydrogen-bonded organic frameworks; self-assembly; ultralong organic phosphorescence; π interactions.
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