THE FIRST FULLY FLUORINATED ORGANICALLY TEMPLATED MATERIALS - SYNTHESIS, STRUCTURES, AND PHYSICAL-PROPERTIES OF [H3N(CH2)(3)NH3]U2F10-CENTER-DOT-2H(2)O, [H3N(CH2)(4)NH3]U2F10-CENTER-DOT-3H(2)O, [H3N(CH2)(6)NH3]U2F10-CENTER-DOT-2H(2)O, AND [HN(CH2CH2NH3)(3)]U5F24

A series of new layered uranium(IV) fluorides have been prepared under hydrothermal conditions from UO2, HF, and H3PO4 by using H2N(CH2)(n)N H2 (n = 3, 4, or 6), and N(CH2CH2NH2)(3) as structure-directing agents . [H3N(CH2)(3)NH3]U2F10. 2H(2)O (UFO-1), [H3N(CH2)(4)NH3]U2F10. 3H(2)O (UFO-2), [H3N(CH2)(6)NH3]U2F10. 2H(2)O (UFO-3), and [HN(CH2CH2NH3)(3) ]U5F24 (UFO-4) have been characterized by single-crystal X-ray diffrac tion, thermogravimetric analysis, BET isotherms, and magnetic suscepti bility measurements. UFO-1, 2, 3,and 4 contain negatively charged uran ium fluoride (UF)layers constructed from linked UF, polyhedra separate d by charge balancing organic cations and occluded water molecules. In UFO-1, 2, and 3, the layers are constructed from equivalent UF9 trica pped trigonal prisms that share three edges and two corners, whereas U FO-4 contains both UF8 bicapped trigonal prisms and UF9 tricapped trig onal prisms. We have demonstrated that the interlamellar organic catio ns in these materials can be ion-exchanged with a large variety of alk ali, alkaline earth, and transition metal cations, thus providing a lo w-temperature route to new condensed mixed metal uranium fluorides. Th e magnetic susceptibility data indicate that UFO-1, 2, and 3 exhibit C urie-Wiess behavior between room temperature and 20 K. [Crystal data: UFO-1, monoclinic, space group P2(1)/c (no. 14), a = 10.715(1) Angstro m, b = 7.097(1) Angstrom, c = 8.767(1) K, beta = 93.804(6)degrees, V= 665.21(1) Angstrom(3) (T = 150 K), Z = 2, R(F) = 5.42%, R-w(F) = 6.79% ,UFO-2, triclinic, space group P (1) over bar (no. 2), a = 12.024(2) A ngstrom, b = 7.149(3)Angstrom c = 8.765(2) Angstrom, a = 90.063(4)degr ees, beta = 107.133(5)degrees, gamma = 92.098(3)degrees, V= 719.49(3) Angstrom(3) (T =150 K), Z = 2, R(F) = 8.05%, R-w(F) = 10.11%; UFO-3, m onoclinic, space group P2(1)/c (no. 14), a = 13.800(2) Angstrom, b = 7 .056(1) Angstrom, c = 8.720(1) Angstrom, beta = 108.338(6)degrees, V = 805.97(2) Angstrom(3) (T = 150 K), Z = 2, R(F) = 3.64%, R-w(F) = 4.65 %; UFO-4, triclinic, space group PT (no. 2), a = 11.534(2) Angstrom, b = 11.532(4) Angstrom, c = 9.634(2) Angstrom, alpha = 104.034(4)degree s, beta = 101.112(8)degrees, gamma = 93.922(4)degrees, V= 1210.9(5) An gstrom(3) (T = 150 K), Z = 2, R(lp)= 6.12%, R-w(F) = 8.19%.].