{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,25]],"date-time":"2025-10-25T11:51:47Z","timestamp":1761393107153,"version":"build-2065373602"},"reference-count":50,"publisher":"Wiley","issue":"17","license":[{"start":{"date-parts":[[2003,8,28]],"date-time":"2003-08-28T00:00:00Z","timestamp":1062028800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2003,9,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The preparation and structural characterization of the novel polyoxoanion [(<jats:italic>\u03b1<\/jats:italic>\u20101,2,3\u2010P<jats:sub>2<\/jats:sub>W<jats:sub>15<\/jats:sub>Ti<jats:sub>3<\/jats:sub>O<jats:sub>62<\/jats:sub>)<jats:sub>4<\/jats:sub>{<jats:italic>\u03bc<\/jats:italic><jats:sub>3<\/jats:sub>\u2010Ti(OH)<jats:sub>3<\/jats:sub>}<jats:sub>4<\/jats:sub>Cl]<jats:sup>45\u2212<\/jats:sup> (<jats:bold>1\u2009a<\/jats:bold>; abbreviated to {TiO<jats:sub>6<\/jats:sub>}<jats:sub>16<\/jats:sub>; FW \u223c16\u2009000) which consists of four tri\u2010Ti<jats:sup>IV<\/jats:sup>\u20101,2,3\u2010substituted <jats:italic>\u03b1<\/jats:italic>\u2010Dawson substructures, four Ti(OH)<jats:sub>3<\/jats:sub> bridging groups, and one encapsulated Cl<jats:sup>\u2212<\/jats:sup> ion, are described. A water\u2010soluble, all\u2010inorganic composition compound of the tetrameric Ti\u2010O\u2010Ti\u2010bridged anhydride form, Na<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>H<jats:sub>45\u2212<jats:italic>x<\/jats:italic><\/jats:sub>[<jats:bold>1\u2009a<\/jats:bold>]<jats:bold>\u22c5<\/jats:bold><jats:italic>y<\/jats:italic>\u2009H<jats:sub>2<\/jats:sub>O (<jats:bold>1<\/jats:bold>; <jats:italic>x<\/jats:italic>=16\u201319, <jats:italic>y<\/jats:italic>=60\u201370), which was afforded by the reaction of the tri\u2010lacunary Dawson polyoxotungstate Na<jats:sub>12<\/jats:sub>[B\u2010<jats:italic>\u03b1<\/jats:italic>\u2010P<jats:sub>2<\/jats:sub>W<jats:sub>15<\/jats:sub>O<jats:sub>56<\/jats:sub>]<jats:bold>\u22c5<\/jats:bold>19\u2009H<jats:sub>2<\/jats:sub>O with an excess of TiCl<jats:sub>4<\/jats:sub> in aqueous solution, was obtained as analytically pure, homogeneous colorless crystals. Single\u2010crystal X\u2010ray structure analysis revealed that <jats:bold>1\u2009a<\/jats:bold> was an inorganic, giant \u201ctetrapod\u201d\u2010shaped molecule (inscribed to a sphere with a diameter of \u223c32 \u00c5) with approximately <jats:italic>T<\/jats:italic><jats:sub>d<\/jats:sub> symmetry, in which the 16 edge\u2010 and\/or corner\u2010shared TiO<jats:sub>6<\/jats:sub> octahedra were contained. This number of TiO<jats:sub>6<\/jats:sub> octahedra was larger than that found in other titanium(<jats:sc>IV<\/jats:sc>)\u2010substituted polyoxotungstates. Complex <jats:bold>1<\/jats:bold> was characterized by complete elemental analysis, TG\/DTA, FTIR, UV\/Vis absorption, and solution (<jats:sup>31<\/jats:sup>P and <jats:sup>183<\/jats:sup>W) NMR spectroscopy. The longest wavelength band in the UV\/Vis absorption spectra of <jats:bold>1<\/jats:bold> in water was attributed to the O\u2192Ti<jats:sup>IV<\/jats:sup> ligand\u2010to\u2010metal charge\u2010transfer (LMCT) transition: the wavelength of the LMCT band increased linearly as the number of TiO<jats:sub>6<\/jats:sub> octahedra contained in the Keggin and Dawson polyoxoanions increased. The Ti<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> chromophores formed in the Keggin and Dawson polyoxotungstates are water\u2010soluble analogues of solid TiO<jats:sub>2<\/jats:sub> or SrTiO<jats:sub>3<\/jats:sub> as light\u2010semiconductors and photocatalysts.<\/jats:p>","DOI":"10.1002\/chem.200305182","type":"journal-article","created":{"date-parts":[[2003,9,2]],"date-time":"2003-09-02T15:37:14Z","timestamp":1062517034000},"page":"4077-4083","source":"Crossref","is-referenced-by-count":79,"title":["Tetrameric, Trititanium(<scp>IV<\/scp>)\u2010Substituted Polyoxotungstates with an <i>\u03b1<\/i>\u2010Dawson Substructure as Soluble Metal\u2010Oxide Analogues: Molecular Structure of the Giant \u201cTetrapod\u201d [(<i>\u03b1<\/i>\u20101,2,3\u2010P<sub>2<\/sub>W<sub>15<\/sub>Ti<sub>3<\/sub>O<sub>62<\/sub>)<sub>4<\/sub>{<i>\u03bc<\/i><sub>3<\/sub>\u2010Ti(OH)<sub>3<\/sub>}<sub>4<\/sub>Cl]<sup>45\u2212<\/sup>"],"prefix":"10.1002","volume":"9","author":[{"given":"Yoshitaka","family":"Sakai","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kenji","family":"Yoza","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chika Nozaki","family":"Kato","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kenji","family":"Nomiya","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,8,28]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19911030107"},{"key":"e_1_2_5_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199100341"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-662-12004-0"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.228.4699.533"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960395y"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0360-0564(08)60041-3"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(95)01141-B"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1381-1169(96)00338-X"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166482.ch3"},{"volume-title":"Polyoxometalate Chemistry from Topology via Self\u2010Assembly to Applications","year":"2001","key":"e_1_2_5_10_2"},{"volume-title":"Polyoxometalate Chemistry for Nano\u2010Composite Design","year":"2002","key":"e_1_2_5_11_2"},{"volume-title":"Inorganic Structural Chemistry","year":"1993","author":"M\u00fcller U.","key":"e_1_2_5_12_2"},{"key":"e_1_2_5_13_2","doi-asserted-by":"crossref","first-page":"735","DOI":"10.1021\/cr00035a013","volume":"95","author":"Linsenbigler A. 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