Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers
authors Shi, FN; Cunha-Silva, L; Ferreira, RAS; Mafra, L; Trindade, T; Carlos, LD; Paz, FAA; Rocha, J
nationality International
journal JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
keywords METAL-ORGANIC FRAMEWORK; EFFECTIVE IONIC-RADII; X-RAY-DIFFRACTION; HIGH-SURFACE-AREA; HYDROTHERMAL SYNTHESIS; MAGNETIC-PROPERTIES; GIANT PORES; STRUCTURAL-CHARACTERIZATION; MOLECULAR-CRYSTALS; POWDER DIFFRACTION
abstract Isostructural modular microporous Na(2)[Y(hedp)(H(2)O)(0.67)] and Na(4)[Ln(2)(hedP)(2)(H(2)O)(2)]center dot nH(2)O (Ln = La, Ce, Nd, Eu, Gd, Tb, Er) framework-type, and layered orthorhombic [Eu(H(2)hedp)(H(2)O)(2)]center dot H(2)O and Na(0.9)[Nd(0.9)Ge(0.10)(Hhedp)(H(2)O)(2)], monoclinic [Ln[H(2)hedp)(H(2)O)]center dot 3H(2)O (Ln = Y, Tb), and triclinic [Yb(H(2)hedp)]center dot H 20 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 Na(4)[Eu(2)(hedP)(2)(H(2)O)(2)]center dot H(2)O 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 Na(4)[Tb(2)(hedP)(2)(H(2)O)2]center dot nH(2)O, affords layered [Tb(H(2)hedp) (H(2)O)]center dot 3H(2)O, whereas layered [Tb(H(2)hedp)(H(2)O)(2)]center dot H(2)O reacts-with sodium chloride yielding a material similar to Na(4)[Tb(2)(hedP)(2)(H(2)O)(2)]center dot nH(2)O. In layered [Y(H(2)hedp)(H(2)O)]center dot 3H(2)O, noncoordinated water molecules are engaged in cooperative waterto-water hydrogen-bonding interactions, leading to the formation of a (H(2)O)(13) cluster, which is the basis of an unprecedented two-dimensional water network present in the interlayer space.
publisher AMER CHEMICAL SOC
issn 0002-7863
year published 2008
volume 130
issue 1
beginning page 150
ending page 167
digital object identifier (doi) 10.1021/ja074119k
web of science category Chemistry, Multidisciplinary
subject category Chemistry
unique article identifier WOS:000252127500035
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journal impact factor 14.357
5 year journal impact factor 13.613
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