Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties

摘要

Four anthracene-based lanthanide metal-organic framework structures (MOFs) were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC) in dimethylformamide (DMF) under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i) {{[Ln2(ADC)3(DMF)4·DMF]}n, Ln = Eu (1) and Tb (2)} and (ii) {{[Ln2(ADC)3(DMF)2(OH2)2·2DMF·H2O]}n, Ln = Er (3) and Tm (4)}. The metal centers exist in various coordination environments; nine coordinate in (i), while seven and eight coordinate in (ii). The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.