Fluorescent Eu3+/Tb3+ Metal-Organic Frameworks for Ratiometric Temperature Sensing Regulated by Ligand Energy

Abstract

This work presents three series of Eu/Tb metal-organic frameworks (MOFs) containing benzophenone-4,4'-dicarboxylic acid (H₂BPNDC), 4,4'-dicarboxydiphenyl ether (H₂OBA), and terephthalic acid (H₂BDC) as the ligands. Eu/Tb MOFs have the same structural features in that their 3D frameworks are simplified as 2,3,10-connected {4².6}₂{4⁶.6¹⁸.8¹⁹.10²}{4}₂ topological networks. The solid-state fluorescence spectra of three Eu/Tb MOF series are attributed to the combined emissions of ⁵D₀ → ⁷F_J (J = 1-4) transitions in Eu³⁺ and ⁵D₄ → ⁷F_J (J = 6-5) transitions in Tb³⁺. The n_Eu:n_Tb of Eu/Tb MOFs is optimized as 1:69 based on the relationships between I_Tb(545)/I_Eu(614) and n_Eu:n_Tb; that is, Eu_0.0143Tb_0.9857-L (L = BPNDC^2-, OBA^2-, and BDC^2-) were selected to carry out the following temperature (T)-sensing tests. The fluorescence mechanism of Eu_0.0143Tb_0.9857-L can be explained by a ligand-to-metal charge transfer combined with an intermetallic Tb³⁺ → Eu³⁺ energy transfer. The T-dependent fluorescence indicates linear relationships with sensitivities of 1.85% K^-1 for Eu_0.0143Tb_0.9857-BPNDC, 6.49% K^-1 for Eu_0.0143Tb_0.9857-OBA, and 0.28% K^-1 for Eu_0.0143Tb_0.9857-BDC. The influence of T on the lowest excited triplet energy levels (T1 values) of the ligands reveals that the ligand energy regulation impacts their fluorescence properties, including the sensitivity, fluorescence quenching rate, quantum yield, and fluorescence lifetime. This shows that Eu_0.0143Tb_0.9857-BPNDC is sufficiently sensitive to T, making it applicable in noncontact T measurements.