Rigid nonlabile polyoxometalate cryptates [ZP[sub 5]W[sub 30]O[sub 110]][sup (15[minus]n)[minus]] that exhibit unprecedented selectivity for certain lanthanide and other multivalent cations

Journal Article · Wed Apr 28 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00061a010· OSTI ID:6258517

Creaser, I; Heckel, M C; Neitz, R J; Pope, M T ^[1]

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1. Georgetown Univ., Washington, DC (United States)

Reaction of aqueous solutions of the heteropolytungstate [NaP[sub 5]W[sub 30]O[sub 110]][sup 14[minus]] with various cations Z[sup n+] in a sealed container at 120-180[degrees]C for several hours leads to cation exchange and the formation of [ZP[sub 5]W[sub 30]O[sub 110]][sup (15-n-)] when Z = Ca[sup 2+], trivalent Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, or Bi, or tetravalent Ce or U. No exchange occurred for Z = Cd[sup 2+], Sn[sup 2+], Tl[sup 3+], Ce[sup 3+], Pr[sup 3+], or Th[sup 4+] at temperatures up to 180[degrees]C. The lanthanide selectivity appears to be determined by ionic radius. The new complexes, which are hydrolytically stable from pH 0 to pH 9--10, are characterized by cyclic voltammetry, IR spectra, and [sup 31]P NMR spectra (single line in all cases except when Z = Y[sup 3+] which shows [sup 2]J([sup 31]P-O-[sup 89]Y) = 1.6 Hz); [delta] = [minus]68.1 to +17.6 ppM. The lanthanide-induced shifts of the [sup 31]P nucleus are predominantly pseudocontact in origin. The [sup 183]W NMR spectrum of the Eu[sup 3+] derivative has four doublets at +62.5, [minus]201.7, [minus]209.5, and [minus]297.5 ppM (1:2:1:1) consistent with the C[sub 5v] structure found for the Na derivative. The emission spectrum of the Eu derivative and the ESR spectrum of the Gd derivative are reported. The low proton relaxivity of the latter complex (ca. 1.0 mM s[sup [minus]1] at 300 MHz) is consistent with the presumed structure in which Gd[sup 3+] is inaccessible to solvent water. 25 refs., 7 figs., 3 tabs.

• OSTI ID: 6258517
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
400702 -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ABSORPTION SPECTROSCOPY
ACTINIDE COMPOUNDS
ACTINIDES
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