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-pyr...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).展开更多
基金supported by the National Natural Science Foundation of China(61136003,61575096,51173081)the Ministry of Education of China(IRT1148),Natural Science Foundation of Jiangsu Province(BM2012010,BK20151512)+2 种基金Priority Academic Program Development of Jiangsu Higher Education Institutions(YX03001)Specialized Research Fund for the Doctoral Program of Higher Education(20113223110005)the National Basic Research Program of China(2012CB933301)
文摘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).
