title: Encapsulation of anion/cation in the central cavity of tetrameric polyoxometalate, composed of four trititanium(IV)-substituted α-Dawson subunits, initiated by protonation/deprotonation of the bridging oxygen atoms on the intramolecular surface.
abstract: Preparation and structural characterization of a novel polyoxometalate (POM), [(P(2)W(15)Ti(3)O(60.5))(4)(NH(4))](35-) 1, i.e., an encapsulated NH(4)(+) cation species in the central cavity of a tetramer (called the Dawson tetramer) constituted by trititanium(IV)-substituted α-Dawson POM substructure, are described. POM 1 was synthesized by several different methods and unequivocally characterized by complete elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), FTIR spectroscopy, solution ((15)N{(1)H}, (31)P, (183)W) NMR spectroscopy, and X-ray crystallography. First, POM 1 was synthesized by a reaction of NH(4)Cl in aqueous solution with a precursor, which was derived by thermal treatment of a monomeric triperoxotitanium(IV)-substituted Dawson POM, [α-1,2,3-P(2)W(15)(TiO(2))(3)O(56)(OH)(3)](9-) 2, for 3 h in an electric furnace at 200 °C. The encapsulated NH(4)(+) cation in 1 was confirmed by (15)N{(1)H} NMR measurement and X-ray crystallography. As another synthesis of 1, a direct exchange of the Cl(-) anion encapsulated in [{α-1,2,3-P(2)W(15)Ti(3)O(57.5)(OH)(3)}(4)Cl](25-) 3 with the NH(4)(+) cation was attained by neutralizing an aqueous solution containing 3 with the addition of aqueous NH(3) (the initial pH of ca. 2-2.5 was changed to 6.4), followed by adding NH(4)Cl. It has been clarified that the conditions as to whether the anion or the cation is encapsulated in the central cavity of the Dawson tetramer were significantly related to the protonation/deprotonation of the bridging oxygen atoms on the intramolecular surface, Ti-O-Ti/Ti-OH-Ti sites constituting the Dawson subunits.
authors.affiliation: Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan.
authors.forename: Yoshitaka
authors.initials: Y
authors.lastname: Sakai
authors.forename: Shuji
authors.initials: S
authors.lastname: Ohta
authors.forename: Yukihiro
authors.initials: Y
authors.lastname: Shintoyo
authors.forename: Shoko
authors.initials: S
authors.lastname: Yoshida
authors.forename: Yuhki
authors.initials: Y
authors.lastname: Taguchi
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Matsuki
authors.forename: Satoshi
authors.initials: S
authors.lastname: Matsunaga
authors.forename: Kenji
authors.initials: K
authors.lastname: Nomiya
mesh_terms: D000838:Anions / Q000737:chemistry; D002214:Capsules / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011522:Protons; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D000838:Anions; D002214:Capsules; D002412:Cations; D009942:Organometallic Compounds; D010100:Oxygen; D011522:Protons; D014025:Titanium; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates