Lanthanide-organic frameworks based on terphenyl-tetracarboxylate ligands:syntheses,structures,optical properties and selective sensing of nitro explosives

Three isostructural three-dimensional （3D） lanthanide-based metal-organic frameworks [Ln2L（H2L）（NMP）2]＇H20 （Ln=Sm（l）, Eu （2）, Gd （3）; H4L= 1,1 ＇：4＇, 1 ＂-terphenyl-2＇,4,4＂,5＇-tetracarboxylic acid; NMP=N-methyl-2-pyrrolidone） have been synthesized and structurally characterized. In 1-3, two Ln3＋ ions are doubly-bridged by two oxygen atoms of two carboxylate groups to form the dinuclear Lnz（Oco ）a unit. Each Ln2（Ocoo ）2 unit links with four H2L2 ligands and four L4- ligands to lead to the 3D framework, which can be rationalized as a new trinodal 4,4,8-connected （44.62）（45.6）（412.616） topological network by considering the dinuclear Ln2（Ocoo ）2 units as 8-connected nodes and L4-/H2L2- ligands as planar 4-connected nodes, respectively. 1 and 3 exhibit blue emission originated from the ligand with the emission maximum at 384 nm, while 2 shows intense characteristic red emission of Eu3＋ ions and weak ligand-centered emission. Moreover, 2 has fluorescent quenching response towards the aromatic nitro compounds, especially for the 3,4-dinitrotoluene （3,4-DNT） with the linear Stern-Volmer relationship in the concentration range of 0-1 mM and the quenching constant （Ksv） of 2.084-103 M 1.

Three isostructural three-dimensional(3D) lanthanide-based metal-organic frameworks [Ln_2L(H_2L)(NMP)_2].H_2O(Ln=Sm(1), Eu(2), Gd(3); H_4L=1,1′:4′,1″-terphenyl-2′,4,4″,5′-tetracarboxylic acid; NMP=N-methyl-2-pyrrolidone) have been synthesized and structurally characterized. In 1–3, two Ln3+ ions are doubly-bridged by two oxygen atoms of two carboxylate groups to form the dinuclear Ln_2(OCOO–)_2 unit. Each Ln_2(OCOO–)_2 unit links with four H_2L^(2-) ligands and four L4. ligands to lead to the 3D framework,which can be rationalized as a new trinodal 4,4,8-connected(44.62)(45.6)(412.616) topological network by considering the dinuclear Ln_2(OCOO–)_2 units as 8-connected nodes and L^4./H_2L^(2-) ligands as planar 4-connected nodes, respectively. 1 and 3 exhibit blue emission originated from the ligand with the emission maximum at 384 nm, while 2 shows intense characteristic red emission of Eu^(3+) ions and weak ligand-centered emission. Moreover, 2 has fluorescent quenching response towards the aromatic nitro compounds, especially for the 3,4-dinitrotoluene(3,4-DNT) with the linear Stern-Volmer relationship in the concentration range of 0–1 mM and the quenching constant(Ksv) of 2.084×10~3 M^(-1).