Lanthanide (III) addition of [Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sup 2-} (Ln=Eu, Dy)

• Published in: Journal of solid state chemistry 2009-10, Vol.182 (10)
• Main Authors: Dang Zhenhua, Graduate School of the Chinese Academy of Sciences, Beijing 100039, Mou Si, Xu Li
• Format: Article
• Language: English
• Subjects: ALKALI METAL COMPOUNDS; ANTIFERROMAGNETISM; CHALCOGENIDES; CHARGED PARTICLES; CRYSTAL STRUCTURE; DYSPROSIUM COMPOUNDS; DYSPROSIUM IONS; ELEMENTS; EUROPIUM COMPOUNDS; HYDROGEN; HYDROGEN COMPOUNDS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; INTERACTIONS; IONS; MAGNETISM; MATERIALS; MATHEMATICS; MINERALS; MOLYBDATES; MOLYBDENUM COMPOUNDS; NONMETALS; OXIDE MINERALS; OXYGEN COMPOUNDS; RADIOACTIVE MATERIALS; RADIOACTIVE MINERALS; RARE EARTH COMPOUNDS; REFRACTORY METAL COMPOUNDS; RUTILE; SODIUM COMPOUNDS; SODIUM IONS; SODIUM SULFIDES; SULFIDES; SULFUR COMPOUNDS; TOPOLOGY; TRANSITION ELEMENT COMPOUNDS; WATER
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2009.07.051

The reactions of LnCl{sub 3}.6H{sub 2}O (Ln=Eu or Dy) and Na{sub 2}[Mo{sub 2}O{sub 3}S(HNTA){sub 2}].6H{sub 2}O afford Na[Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sub 2}.Eu(H{sub 2}O){sub 9}.3H{sub 2}O (1) (NTA=nitrilotriacetate) and Na{l_brace}(H{sub 2}O){sub 6}Dy[Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sub 2}{r_brace}.7.5H{sub 2}O (2), respectively. The [Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sup 2-} cluster units of 1 are interconnected by Na{sup +} into a 3-D open framework with rutile topology templated by Eu(H{sub 2}O){sub 9}{sup 3+}. The coordination of [Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sup 2-} to the slightly smaller Dy{sup 3+} ion of greater ionic potential as a consequence of lanthanide contraction has been observed to form the pentanuclear heterometallic {l_brace}Dy(H{sub 2}O){sub 6}[Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sub 2}{r_brace}{sup -}, which is linked by Na{sup +} and hydrogen bonds between the protonated carboxylate groups into a 3-D supramolecular framework. The weak antiferromagnetic interactions between the Dy{sup 3+} ions of 2 have been observed. - Graphical abstract: The reactions of LnCl{sub 3} and Na{sub 2}[Mo{sub 2}O{sub 3}S(HNTA){sub 2}] result in the 3-D open framework of Na[Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sub 2} templated by Eu(H{sub 2}O){sub 9}{sup 3+} (1) and the pentanuclear heterometallic cluster Na{l_brace}(H{sub 2}O){sub 6}Dy[Mo{sub 2}O{sub 3}S(HNTA){sub 2}]{sub 2}{r_brace} (2) as a consequence of lanthanide contraction.