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Self-assembly of lanthanide(iii) coordination polymers from a bifunctional 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate ligand with the assistance of oxalate: syntheses, structures, luminescence, and magnetic properties.

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Title: Self-assembly of lanthanide(iii) coordination polymers from a bifunctional 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylate ligand with the assistance of oxalate: syntheses, structures, luminescence, and magnetic properties.
Authors: Zhang, Li-Yang1, Lu, Li-Ping1, Zhu, Miao-Li1,2, Feng, Si-Si1,2
Source: CrystEngComm. 4/14/2017, Vol. 19 Issue 14, p1953-1964. 12p.
Subjects: Bifunctional catalysis, Pyridine derivatives, Imidazoles, Chemical synthesis, Coordination polymers, Rare earth metals, Magnetic properties
Abstract: Based on a bifunctional 2-(pyridine-2-yl)-1H-4,5-imidazole-dicarboxylic acid ligand, a novel family of lanthanide coordination polymers with formulas [Ln(HPIDC)(C2O4)0.5(H2O)]n (Ln = La, 1; Ce, 2) and [Ln2(HPIDC)(C2O4)2(H2O)3]n·2nH2O (Ln = Pr, 3; Nd, 4; Sm, 5; Eu, 6; Gd, 7; Tb, 8; Dy, 9; Ho, 10; Er, 11), (H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid & H2C2O4 = oxalic acid) has been prepared under hydro-solvothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermogravimetric analysis. Notably, the ligands adopt the same μ3-kN,O:kO′,O′′:kO′′′ conformation in all compounds, which brings about two types of isostructural lanthanide coordination polymers. Namely, 1 and 2 crystallize in the monoclinic space group P21/n and are composed of [Ln2(COO)2] dinuclear subunits with networks having the symbol (63·82·10)2(63)2(8). Meanwhile, 3–11 crystallize in the monoclinic space group P21/c and are constructed with tetranuclear [Ln4(COO)4] subunits with networks having the symbol (103)2(104·122)(10)2. The photoluminescence measurement indicates that Eu(iii) and Tb(iii) coordination polymers show very strong reddish-orange and green emission bands with CIE chromaticity coordinates (0.612, 0.325) and (0.284, 0.523) and quantum yields of 54.3% & 34.7%, respectively. The magnetic properties of 3 and 7–11 are investigated, and the results indicate a ferromagnetic interaction between Gd(iii) magnetic centers in complex 7 and antiferromagnetic interactions in other complexes. [ABSTRACT FROM AUTHOR]
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Abstract:Based on a bifunctional 2-(pyridine-2-yl)-1H-4,5-imidazole-dicarboxylic acid ligand, a novel family of lanthanide coordination polymers with formulas [Ln(HPIDC)(C2O4)0.5(H2O)]n (Ln = La, 1; Ce, 2) and [Ln2(HPIDC)(C2O4)2(H2O)3]n·2nH2O (Ln = Pr, 3; Nd, 4; Sm, 5; Eu, 6; Gd, 7; Tb, 8; Dy, 9; Ho, 10; Er, 11), (H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid & H2C2O4 = oxalic acid) has been prepared under hydro-solvothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermogravimetric analysis. Notably, the ligands adopt the same μ3-kN,O:kO′,O′′:kO′′′ conformation in all compounds, which brings about two types of isostructural lanthanide coordination polymers. Namely, 1 and 2 crystallize in the monoclinic space group P21/n and are composed of [Ln2(COO)2] dinuclear subunits with networks having the symbol (63·82·10)2(63)2(8). Meanwhile, 3–11 crystallize in the monoclinic space group P21/c and are constructed with tetranuclear [Ln4(COO)4] subunits with networks having the symbol (103)2(104·122)(10)2. The photoluminescence measurement indicates that Eu(iii) and Tb(iii) coordination polymers show very strong reddish-orange and green emission bands with CIE chromaticity coordinates (0.612, 0.325) and (0.284, 0.523) and quantum yields of 54.3% & 34.7%, respectively. The magnetic properties of 3 and 7–11 are investigated, and the results indicate a ferromagnetic interaction between Gd(iii) magnetic centers in complex 7 and antiferromagnetic interactions in other complexes. [ABSTRACT FROM AUTHOR]
ISSN:14668033
DOI:10.1039/c7ce00149e