On the modulation/energy competing of Tb(III)/Eu(III) emission in microporous MOF host for peroxide recognition

Being an important chemical reagent having moderate oxidizability, peracitic acid (PAA) has been applied in modern industries and processing, as well as public safety. These versatile applications make PAA an important analyte to be precisely and sensitively detected. The present work chose the combination of rare-earth-based probe and a microporous host bio-MOF-1 ([Zn₈(ad)₄(BPDC)₆O·2(Me₂NH₂)⁺]·G, ad = adenine, BPDC = 4,4'-biphenyl dicarboxylic acid, G = N,N-dimetylformamide and water). Two β-diketone ligands, 1,3-di(pyridin-3-yl)propane-1,3-dione (DPY) and 1,3-diphenylpropane-1,3-dione (DPP), were coordinated to Tb(III) and Eu(III) ions to form probe [RE(DPY/DPP)₂]Cl which was loaded into bio-MOF-1 micropores with different loading contents via an ionic exchange operation. The resulting composite samples were fully characterized, including synthesis, morphology, composition, sensing performance and mechanism. The protonation/oxidization of DPY and DPP ligands adjusted their triplet energy level (T₁) and consequently affected their energy transfer (ET) efficiency to RE ions, resulting in the variation of RE emission relative intensity. A new pathway for PAA optical sensing was thus proposed. Linear fitting equations were observed for DPY-based samples, showing fluorescence intensity ratio value of 8.80, response time of 9 s, and LOD of 8.08 μM within working region of 0-140 μM.