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.

IV)-Substituted α-Dawson Subunits, Initiated by Protonation/Deprotonation of the Bridging Oxygen Atoms on the Intramolecular Surface. -The [(P2W15Ti3O60.5)4(NH4)] 35-Dawson tetramer with encapsulated cation is synthesized and characterized by FTIR, 15 N{ 1 H}, 31 P, and 183 W NMR spectroscopy. Single crystal XRD shows that (III) crystallizes in the triclinic space group P1 with Z = 4. -(SAKAI, Y.; OHTA, S.; SHINTOYO, Y.; YOSHIDA, S.; TAGUCHI, Y.; MATSUKI, Y.; MATSUNAGA, S.; NOMIYA*, K.; Inorg. Chem. 50 (2011) 14, 6575-6583, http://dx.doi.org/10.1021/ic200355e ; Dep. Chem., Fac. Sci., Kanagawa Univ., Hiratsuka, Kanagawa 259-12, Japan; Eng.) -W. Pewestorf 37-018 NH + 4