Interconvertable Modular Framework and Layered Lanthanide(III)-Etidronic Acid Coordination Polymers
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- 作者：F. N. Shi ; L. Cunha-Silva ; R. A. Sá ; Ferreira ; L. Mafra ; T. Trindade ; L. D. Carlos ; F. A. Almeida Paz ; J. Rocha
- 刊名：Journal of the American Chemical Society
- 出版年：2008
- 出版时间：January 9, 2008
- 年：2008
- 卷：130
- 期：1
- 页码：150 - 167
- 全文大小：1768K
- 年卷期：v.130,no.1(January 9, 2008)
- ISSN：1520-5126
文摘
Isostructural modular microporous Na2[Y(hedp)(H2O)0.67] and Na4[Ln2(hedp)2(H2O)2]·nH2O (Ln= La, Ce, Nd, Eu, Gd, Tb, Er) framework-type, and layered orthorhombic [Eu(H2hedp)(H2O)2]·H2O andNa0.9[Nd0.9Ge0.10(Hhedp)(H2O)2], monoclinic [Ln(H2hedp)(H2O)]·3H2O (Ln = Y, Tb), and triclinic [Yb(H2hedp)]·H2O coordination polymers based on etidronic acid (H5hedp) have been prepared by hydrothermalsynthesis and characterized structurally by (among others) single-crystal and powder X-ray diffraction andsolid-state NMR. The structure of the framework materials comprises eight-membered ring channels filledwith Na+ and both free and lanthanide-coordinated water molecules, which are removed reversibly bycalcination at 300 C (structural integrity is preserved up to ca. 475 C), denoting a clear zeolite-type behavior.Interesting photoluminescence properties, sensitive to the hydration degree, are reported for Na4[Eu2(hedp)2(H2O)2]·H2O and its fully dehydrated form. The 3D framework and layered materials are, to a certain extent,interconvertable during the hydrothermal synthesis stage via the addition of HCl or NaCl: of the 3Dframework Na4[Tb2(hedp)2(H2O)2]·nH2O, affords layered [Tb(H2hedp) (H2O)]·3H2O, whereas layered [Tb(H2hedp)(H2O)2]·H2O reacts with sodium chloride yielding a material similar to Na4[Tb2(hedp)2(H2O)2]·nH2O.In layered [Y(H2hedp)(H2O)]·3H2O, noncoordinated water molecules are engaged in cooperative water-to-water hydrogen-bonding interactions, leading to the formation of a (H2O)13 cluster, which is the basis ofan unprecedented two-dimensional water network present in the interlayer space.