Tb and Eu in MOF‐76: Elucidating the Mechanisms Responsible for the Divergent Excellent and Poor Photoluminescence Quantum Yields

Abstract

Metal–organic frameworks (MOFs) have emerged as promising hosts for lanthanide ions owing to their ability to sensitize the lanthanides and provide a rigid topology while still permitting interactions with guest species. Among these lanthanide MOFs, MOF‐76 is a noteworthy example composed of 1,3,5‐benzenetricarboxylic acid (H3BTC) and lanthanide ions. In this study, a high photoluminescence quantum yield (ΦPL) of 91% for Tb‐based MOF‐76 (Tb‐MOF) is reported, while the efficiency of Eu‐based MOF‐76 (Eu‐MOF) is over five times lower. A potential circumvention of the poor performance of Eu3+ is energy transfer from Tb3+ to Eu3+, but it is found that although energy transfer is efficient the ΦPL of the Eu3+ remains low. The study investigates the cause of the lower quantum yield in Eu‐MOF by ruling out possible factors such as crystal size, guest solvent molecules, and energy transfer from or back to the linker. None of these are significant loss mechanisms, leading to conclude that the MOF‐76 ligand unfortunately leads to fast non‐radiative deactivation of the Eu3+ excited state. The results suggest that MOF‐76 is an excellent host for Tb3+ ions, but exploration is required for MOF linkers to simply access the potentially excellent emission efficiency of Eu3+ ions.