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By using a semi-rigid tripodal ligand 5-(4-carboxybenzyloxy)isophthalic acid (H₃L) and lanthanide metal ions (Nd³⁺, Tb³⁺), two novel lanthanide metal&#8211;organic frameworks, namely, {[Nd₂L₂(DMF)4] DMF}_n (<b>1</b>), and {TbL(DMF)(H₂O)}_n (<b>2</b>), were synthesized under mild solvothermal conditions and structurally characterized by X-ray single crystal diffraction. Compounds <b>1</b> and <b>2</b> are isostructural, in which L^3&#8211; ligands linked dinuclear lanthanide metal&#8211;carboxylate units to form non-interpenetrated 3D network with (3,6)-connected topology. Luminescent investigations reveal that compound <b>1</b> displays the near-infrared emission at room temperature, and compound <b>2</b> can be employed as selective probe for Cr₂O₇²^&#8722; anion in aqueous solution based on luminescence quenching. Moreover, compound <b>2</b> exhibits catalytic activity for cyclo-addition of CO₂ and epoxides under relatively mild conditions.