title: Synthesis and structural characterization of inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates.
abstract: Three inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates with organic linkers of different lengths, TBA8[{(γ-H2SiW10O36Pd2)(O2C(CH2)nCO2)}2] (n = 1 (II), 3 (III), and 5 (IV), TBA = [(n-C4H9)4N](+)), were synthesized by exchange of the acetate ligands in TBA4[γ-H2SiW10O36Pd2(OAc)2] (ITBA) with malonic, glutaric, and pimelic acids, respectively. The X-ray crystallographic analysis of II, IIIA (IIIA: III with DCE, DCE = 1,2-dichloroethane), and IVA (IVA: IV with 10DCE) revealed that the anion parts of II, IIIA, and IVA were inorganic-organic-inorganic hybrids composed of two dipalladium-substituted γ-Keggin silicodecatungstates connected by two dicarboxylate ligands. In the crystal structure of IVA, 10 DCE molecules per polyanion were present in the vicinity of polyanions. Compound IVB (IVB: IV with 0.2DCE) was obtained by the evacuation of IVA. The DCE sorption-desorption isotherms of IVB showed that the amount of DCE sorbed was saturated at 10.5 mol mol(-1), of which the amount was close to that (10 mol mol(-1)) of crystallographically assigned DCE molecules. In the DCE sorption-desorption isotherms, a low-pressure hysteresis was observed probably because of hydrogen-bonding interaction between DCE molecules and polyanions. The powder X-ray diffraction (XRD) pattern of IVA changed with decrease in the relative DCE vapor pressure to form IVC (IVC: IV with 0.7DCE) at P/P0 = 0.0. The in situ powder XRD study showed reversible structure transformation between IVA and IVC driven by the sorption-desorption of DCE.
authors: Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
authors: Tomohisa
authors: T
authors: Hirano
authors: Kazuhiro
authors: K
authors: Uehara
authors: Sayaka
authors: S
authors: Uchida
authors: Mitsuhiro
authors: M
authors: Hibino
authors: Keigo
authors: K
authors: Kamata
authors: Noritaka
authors: N
authors: Mizuno
mesh_terms: D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D017646:Organosilicon Compounds; D017973:Tungsten Compounds; D010165:Palladium