| 3-sulfobenzoatic acid, 1,2-phenylenedioxydiacetic acid, 2,2'-diphenyldicarboxylatic acid and derivations of benzoic acid were chose and eigthteen single crystals of lanthanide carboxylate complexes were obtained by hydrothermal and solvent methods, which have not been reported by literatures. The structures and properties were characterized through X-ray single-crystal diffraction, elemental analysis, IR spectrometry, fluorescence spectrometry and DTA-TGA. The following is the main results:1. 3-sulfobenzoatic acid as the ligand, and rare lanthanide micropore cluster polymer complexes were prepared by hydrothermal method: {[Ln<sub>4(3-SBA)4(μ3-OH)4(H2O)4]·mH2O}n (Ln = Eu (1), m = 10; Ln = Tb (2), m = 8; Ln = Dy (3), m = 10; Ln = Gd (4), m = 10; Ln = Nd (5), m = (10), {[Tb4(3-SBA)4(μ3-OH)4(phen)3(H2O)3]·7H2O}n (6) (3-SBA = 3-sulfobenzoate, phen = 1,10-phenanthroline). The complexes 1-5 are isomorphous with similar crystal structures. The five complexes containing cubane-like clusters [Ln4(μ3-OH)4(H2O)3]8+ (Ln = Eu, Tb, Dy, Gd, Nd) and 3-SBA ligands as linkages to assemble the 3-D network structure, respectively. The complex 6 containing cubane-like clusters [Tb4(μ3-OH)4(phen)3(H2O)3]8+ and 3-SBA ligands as linkages to assemble the 2-D network structure.2. 1,2-phenylenedioxydiacetic acid as the ligand, three rare 1-D double chain lanthanide complexes were prepared by solvent method for the first time: {[Ln(PDOA)1.5(H2O)3]··H2O}n (Ln = Sm (1), Eu (), Dy (3)). And other two complexes were obtained by solvent method too: [Tb2(PDOA)3(H2O)6]·2H2O (4), [La(H2PDOA)(PDOA)(OH)(H2O)]·5H2O (5) (PDOA = 1, 2-phenylenedioxydiacetate). The complexes 1-3 are isomorphous with unusual 1-D double chain structures. The complex 4 is a dimer. In the binuclear molecule, the two Tb3+ ions are linked by only one PDOA ligand through its two bidentate-chelating carboxylate groups. And the other two PDOA ligands act as a terminal ligand using two monodentate carboxylate oxygen and ether oxygen atoms to chelate one Tb3+ ion, respectively. The complex 5 is a mononuclear structure, the coordination number of center La3+ ion is ten.3. 2,2'-diphenyldicarboxylatic acid and derivations of benzoic acid as the ligands, seven new lanthanide complexes were prepared by hydrothermal and solvent methods: [Sm2(dpdc)3(H2O)2]n (1), [Dy2(dpdc)3(H2O)2]n (), {[Eu(,4-DFBA)3·(H2O)2]·H2O}n (3), [Eu(,3-DFBA)3·(H2O)2]n (4), [Tb(4-BrBA)2(phen)(NO3)]2 (5), [Tb(4-BrBA)3(2,2'-bipy)(H2O)]2·2H2O (6) and [Eu(2,5-DFBA)3(2,2'-bipy)]2 (7) (dpdc = 2,2'-diphenyldicarboxylate, 2,4-DFBA = 2,4-difluorobenzoate, 2,3-DFBA = 2,3- difluorobenzoate, 4-BrBA = 4-bromobenzoate, 2,5-DFBA = 2,5-difluorobenzoate, phen = 1,10-phenanthroline, 2,2'-bipy = 2,2'-bipyridine). |
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