Multifunctional Zn–Ln (Ln = Eu and Tb) heterometallic metal–organic frameworks with highly efficient I2 capture, dye adsorption, luminescence sensing and white-light emission

Abstract

A new family of isostructural 3d–4f heterometallic metal–organic frameworks (HMOFs), [Zn₃Eu_xTb_2−x(TZI)₄(DMA)₅(H₂O)₃]·4DMA [x = 0 (1), 0.3 (2), 0.6 (3), 0.9 (4), 1 (5), 1.2 (6), 1.5 (7), 1.8 (8), 2 (9)], has been synthesized using the 5-(4-(tetrazol-5-yl) phenyl)isophthalic acid (H₃TZI) ligand, Ln^III ions and Zn^II ions under solvothermal conditions. All HMOFs exhibit a (3,3,4,5,5)-connected 6³·6³(4²·6²·8²)(4·6⁵·8)(4·6⁶·8³) topology, which features three different types of motifs: one is a mononuclear Zn^II ion and the other two motifs are binuclear [Zn(COO)₃Ln] clusters. The adsorption experiments indicate that Zn₃Tb₂ (1) could efficiently remove almost all I₂ from cyclohexane solution after 12 h and also showed better adsorption towards neutral red (NR) dye (adsorption: only the Zn₃Tb₂ (1) was taken as one representative). Simultaneously, the luminescence sensing showed that Zn₃Tb₂ (1) and Zn₃Eu₂ (9) have excellent response and sensitivity towards pollutants such as Fe³⁺ ions and 2,4,6-trinitrophenol (TNP) with high selectivity and a fairly low limit of detection through luminescence quenching effect. Moreover, seven trimetallic-doped HMOFs 2–8 analogues of Zn₃Ln₂ (single) HMOFs were designed and prepared, showing different changes of luminescent color. More interestingly, Zn₃Eu_1.5Tb_0.5 (7) with white-light emission was fabricated by doping relative concentrations of Eu³⁺ and Tb³⁺ ions. To the best of our knowledge, Zn₃Eu_1.5Tb_0.5 (7) represents a novel kind of heterometallic Zn₃Ln₂ HMOFs with white-light emission. It could be deduced that the excellent characteristics, namely strong typical luminescence emission of Zn^II and Ln^III ions, microporous channels, active open metal sites (tetra-coordinated Zn^II–metal sites), and uncoordinated carboxylate O atoms and uncoordinated tetrazolate N atoms, made the above HMOFs an ideal platform for adsorption, luminescence sensing, and white-light emission. More significantly, these HMOFs are the first reported Zn–Ln heterometallic materials with the H₃TZI ligand.