Complexes of lanthanoid salts with macrocyclic ligands. Part 32. Synthesis and characterization of the complexes between lanthanoid nitrates and a tetraoxadiaza macrocycle |
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| Institution: | 1. Crop Biotech Institute and Graduate School of Biotechnology, Kyung Hee University, Yongin 17104, Korea;2. Plant Systems Engineering Research Center, Korea Research Institute of Bioscience and Biotechnology, Daejeon 34141, Korea;1. State Key Laboratory of Organic-Inorganic Composites, Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029, China;2. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, China;1. University of Birmingham, Edgbaston, Birmingham B152TT, UK;2. University of Chile, Av. Diagonal Paraguay 257, Santiago, Chile;1. Kenya Forestry Research Institute (KEFRI), Headquarters, Nairobi, Kenya;2. Kenyatta University, Department of Environmental Sciences, School of Environmental Sciences, Nairobi, Kenya;1. Key Laboratory of Coastal Science and Integrated Management, First Institute of Oceanography, Ministry of Natural Resources, Qingdao, Shandong Province 266061, China;2. Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment, Nanjing, Jiangsu Province 210042, China;1. Institut UTINAM (UMR CNRS 6213), Université de Bourgogne-Franche-Comté, 16 Route de Gray, 25030 Besançon Cedex, France;2. Institut de Science des Matériaux de Mulhouse (IS2M-UMR CNRS 7361), Université de Haute-Alsace, 15 Rue Jean Starcky, BP 2488, 68057 Mulhouse Cedex, France |
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| Abstract: | Lanthanoid nitrates react with 1,7,10,16-tetraoxa- 4,13-diaza-N,N′-dimethylcyclooctadecane, Me2(2,2), to give complexes with two different metal:ligand ratios, 1:1 (Ln = La, Ce, Tb) and 4:3 (Ln = Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho). The complexes were isolated from anhydrous solutions in acetonitrile and characterized by elemental analysis, X-ray diffraction, magnetic susceptibility measurements and vibrational analysis.The La and Ce 1:1 complexes are non-ionic and probably 12-coordinated, with the metal ion bound to the six donor atoms of the ligand and to three bidentate nitrate ions. The 4:3 complexes are ionic; they contain three bis(nitrato) complex cations Ln(NO3)2·Me2(2,2)]+ and one hexakis(nitrato) anion Ln(NO3)6]3?. Spectroscopic data, including luminescence spectra, point to the 1:1 Tb-complex as being a 4:3 complex with an additional outer-sphere coordinated molecule of ligand.In solution, the 1:1 complexes remain essentially non-ionic, although some dissociation cannot be ruled out, whereas the 4:3 complexes behave as 2:1 (of even 3:1) electrolytes. |
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