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Shi FN, Cunha-Silva L, Ferreira RA, et al. Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers. J Am Chem Soc. 2007;130(1):150-67doi: 10.1021/ja074119k.
Shi, F. N., Cunha-Silva, L., Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A., & Rocha, J. (2008). Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers. Journal of the American Chemical Society, 130(1), 150-67. https://doi.org/10.1021/ja074119k
Shi, F N, et al. "Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers." Journal of the American Chemical Society vol. 130,1 (2008): 150-67. doi: https://doi.org/10.1021/ja074119k
Shi FN, Cunha-Silva L, Ferreira RA, Mafra L, Trindade T, Carlos LD, Paz FA, Rocha J. Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers. J Am Chem Soc. 2008 Jan 09;130(1):150-67. doi: 10.1021/ja074119k. Epub 2007 Dec 13. PMID: 18076163.
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J Am Chem Soc. 2008 Jan 09;130(1):150-67. doi: 10.1021/ja074119k. Epub 2007 Dec 13.

Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers.

Journal of the American Chemical Society

F N Shi, L Cunha-Silva, R A Sa Ferreira, L Mafra, T Trindade, L D Carlos, F A Almeida Paz, J Rocha

Affiliations

  1. Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal.

PMID: 18076163 DOI: 10.1021/ja074119k

Abstract

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 and Na0.9[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 hydrothermal synthesis and characterized structurally by (among others) single-crystal and powder X-ray diffraction and solid-state NMR. The structure of the framework materials comprises eight-membered ring channels filled with Na+ and both free and lanthanide-coordinated water molecules, which are removed reversibly by calcination at 300 degrees C (structural integrity is preserved up to ca. 475 degrees 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 3D framework 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 of an unprecedented two-dimensional water network present in the interlayer space.

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