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Herein, an \u03b1\u2010Dawson\u2010type silicotungstate, TBA\n                    <jats:sub>8<\/jats:sub>\n                    [\u03b1\u2010Si\n                    <jats:sub>2<\/jats:sub>\n                    W\n                    <jats:sub>18<\/jats:sub>\n                    O\n                    <jats:sub>62<\/jats:sub>\n                    ]\n                    <jats:bold>\u22c5<\/jats:bold>\n                    3\u2009H\n                    <jats:sub>2<\/jats:sub>\n                    O (\n                    <jats:bold>II<\/jats:bold>\n                    ) that possesses a \u22128 charge was successfully synthesized by dimerization of a trivacant lacunary \u03b1\u2010Keggin\u2010type silicotungstate TBA\n                    <jats:sub>4<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    [\u03b1\u2010SiW\n                    <jats:sub>9<\/jats:sub>\n                    O\n                    <jats:sub>34<\/jats:sub>\n                    ]\n                    <jats:bold>\u22c5<\/jats:bold>\n                    2\u2009H\n                    <jats:sub>2<\/jats:sub>\n                    O (\n                    <jats:bold>I<\/jats:bold>\n                    ) in an organic solvent. POM\n                    <jats:bold>II<\/jats:bold>\n                    could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus\u2010centered POM TBA\n                    <jats:sub>6<\/jats:sub>\n                    [\u03b1\u2010P\n                    <jats:sub>2<\/jats:sub>\n                    W\n                    <jats:sub>18<\/jats:sub>\n                    O\n                    <jats:sub>62<\/jats:sub>\n                    ]\u22c5H\n                    <jats:sub>2<\/jats:sub>\n                    O (\n                    <jats:bold>III<\/jats:bold>\n                    ) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal \u03bc\n                    <jats:sub>3<\/jats:sub>\n                    \u2010oxygen atoms were increased by changing the central heteroatoms from P\n                    <jats:sup>5+<\/jats:sup>\n                    to Si\n                    <jats:sup>4+<\/jats:sup>\n                    , thereby supporting the protonation of\n                    <jats:bold>II<\/jats:bold>\n                    . Additionally,\n                    <jats:bold>II<\/jats:bold>\n                    showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than\n                    <jats:bold>I<\/jats:bold>\n                    and\n                    <jats:bold>III<\/jats:bold>\n                    .\n                  <\/jats:p>","DOI":"10.1002\/chem.201400390","type":"journal-article","created":{"date-parts":[[2014,4,2]],"date-time":"2014-04-02T11:53:20Z","timestamp":1396439600000},"page":"5946-5952","source":"Crossref","is-referenced-by-count":52,"title":["Synthesis of \u03b1\u2010Dawson\u2010Type Silicotungstate [\u03b1\u2010Si\n                    <sub>2<\/sub>\n                    W\n                    <sub>18<\/sub>\n                    O\n                    <sub>62<\/sub>\n                    ]\n                    <sup>8\u2212<\/sup>\n                    and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds"],"prefix":"10.1002","volume":"20","author":[{"given":"Takuo","family":"Minato","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kosuke","family":"Suzuki","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Keigo","family":"Kamata","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Noritaka","family":"Mizuno","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,4,2]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(95)01141-B"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0360-0564(08)60041-3"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166482.ch3"},{"key":"e_1_2_6_5_2","unstructured":"Thematic issue on POMs (Ed.:\u2005C.\u2005L. 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