Lanthanide (III) addition of [Mo2O3S(HNTA)2]2− (Ln=Eu, Dy)

The reactions of LnCl3·6H2O (Ln=Eu or Dy) and Na2[Mo2O3S(HNTA)2]·6H2O afford Na[Mo2O3S(HNTA)2]2·Eu(H2O)9·3H2O (1) (NTA=nitrilotriacetate) and Na{(H2O)6Dy[Mo2O3S(HNTA)2]2}·7.5H2O (2), respectively. The [Mo2O3S(HNTA)2]2− cluster units of 1 are interconnected by Na+ into a 3-D open framework with rutile topology templated by Eu(H2O)93+. The coordination of [Mo2O3S(HNTA)2]2− to the slightly smaller Dy3+ ion of greater ionic potential as a consequence of lanthanide contraction has been observed to form the pentanuclear heterometallic {Dy(H2O)6[Mo2O3S(HNTA)2]2}−, which is linked by Na+ and hydrogen bonds between the protonated carboxylate groups into a 3-D supramolecular framework. The weak antiferromagnetic interactions between the Dy3+ ions of 2 have been observed.

The reactions of LnCl3 and Na2[Mo2O3S(HNTA)2] result in the 3-D open framework of Na[Mo2O3S(HNTA)2]2 templated by Eu(H2O)93+ (1) and the pentanuclear heterometallic cluster Na{(H2O)6Dy[Mo2O3S(HNTA)2]2} (2) as a consequence of lanthanide contraction.Figure optionsDownload as PowerPoint slide