Utilization of cyclopentylamine as structure-directing agent for the formation of fluorinated gallium phosphates exhibiting extra-large-pore open frameworks with 16-ring (ULM-16) and 18-ring channels (MIL-46)

作者：Sassoye C; Marrot J; Loiseau T^*; Ferey G

来源：Chemistry of Materials, 2002, 14(3): 1340-1347.

DOI：10.1021/cm011247d

Two fluorinated gallium phosphates, Ga-4(PO4)(4)F-1.33(OH)(0.67).1.5NC(5)H(12).0.5H(3)O-0.5H(2)O (ULM-16) and Ga-9(PO4)(8)F-7.3(OH)(0.2).4NC(5)H(12).0.5H(3)O.3.5H(2)O (MIL-46), have been hydrothermally synthesized by varying the fluorine amount in the presence of cyclopentylamine as structure-directing agent (at 180 degreesC for 3 days). Their structures were determined by means of single-crystal X-ray diffraction. The first compound (obtained with low fluorine concentration) is isostructural to the gallium phosphate ULM-16 previously prepared with cyclohexylamine. Its three-dimensional framework is built up from the connection by corner sharing of the hexameric units Ga-3(PO4)(3)F-2 together with the tetramer Ga-2(PO4)(2) and consists of channels bound by 16 polyhedra inserting the protonated cyclopentylamine. The second phase (prepared with high fluorine concentration) exhibits a new three-dimensional topology based on the condensation by corner sharing of the identical hexameric building block Ga-3(PO4)(3)F-2 with a pentameric species Ga-3(PO4)(2)F-4. The resulting network is composed of large 18-ring channels hosting the protonated cyclopentylamine and water molecules. Crystal data are as follows: Ga-4(PO4)(4)F-1.33(OH)(0.67).1.5NC(5)H(12).0.5H(3)O.0.5H(2)O (ULM-16), orthorhombic, Pbcn (no. 60), a = 27.316(5) Angstrom, b = 17.472(3) Angstrom, c = 10.1970(14) Angstrom, V = 4866.7(14) Angstrom(3) and Z = 8; Ga-9(PO4)(8)F-7.3(OH)(0.2).4NC(5)H(12).0.5H(3)O.3.5H(2)O (MIL-46) orthorhombic, Pnnm (no. 58), a = 10.2735(2) Angstrom, b = 18.5962(3) Angstrom, c = 29.6279(2) Angstrom, V = 5660.4(2) Angstrom(3), Z = 4.

• 出版日期2002-3