{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,2]],"date-time":"2025-11-02T16:38:51Z","timestamp":1762101531733,"version":"build-2065373602"},"reference-count":52,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2014,3,6]],"date-time":"2014-03-06T00:00:00Z","timestamp":1394064000000},"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":[[2014,3,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Nanoscale uranyl peroxide clusters containing UO<jats:sub>2<\/jats:sub><jats:sup>2+<\/jats:sup> groups bonded through peroxide bridges to form polynuclear molecular species (polyoxometalates) exist both in solution and in the solid state. There is an extensive family of clusters containing 28\u2005uranium atoms (U<jats:sub>28<\/jats:sub> clusters), with an encapsulated anion in the center, for example, [UO<jats:sub>2<\/jats:sub>(O<jats:sub>2<\/jats:sub>)<jats:sub>3\u2212<jats:italic>x<\/jats:italic><\/jats:sub>(OH)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub><jats:sup>4\u2212<\/jats:sup>], [Nb(O<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub><jats:sup>3\u2212<\/jats:sup>], or [Ta(O<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub><jats:sup>3\u2212<\/jats:sup>]. The negative charge of these clusters is balanced by alkali ions, both encapsulated, and located exterior to the cluster. The present study reports measurement of enthalpy of formation for two such U<jats:sub>28<\/jats:sub> compounds, one of which is uranyl centered and the other is peroxotantalate centered. The [(Ta(O<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>]\u2010centered U<jats:sub>28<\/jats:sub> capsule is energetically more stable than the [(UO<jats:sub>2<\/jats:sub>)(O<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>]\u2010centered capsule. These data, along with our prior studies on other uranyl\u2013peroxide solids, are used to explore the energy landscape and define thermochemical trends in alkali\u2013uranyl\u2013peroxide systems. It was suggested that the energetic role of charge\u2010balancing alkali ions and their electrostatic interactions with the negatively charged uranyl\u2013peroxide species is the dominant factor in defining energetic stability. These experimental data were supported by DFT calculations, which agree that the [(Ta(O<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>]\u2010centered U<jats:sub>28<\/jats:sub> capsule is more stable than the uranyl\u2010centered capsule. Moreover, the relative stability is controlled by the interactions of the encapsulated alkalis with the encapsulated anion. Thus, the role of alkali\u2010anion interactions was shown to be important at all length scales of uranyl\u2013peroxide species: in both comparing clusters to clusters; and clusters to monomers or extended solids.<\/jats:p>","DOI":"10.1002\/chem.201304076","type":"journal-article","created":{"date-parts":[[2014,3,6]],"date-time":"2014-03-06T16:02:18Z","timestamp":1394121738000},"page":"3646-3651","source":"Crossref","is-referenced-by-count":23,"title":["The Energy Landscape of Uranyl\u2013Peroxide Species"],"prefix":"10.1002","volume":"20","author":[{"given":"Eitan","family":"Tiferet","sequence":"first","affiliation":[]},{"given":"Adri\u00e0","family":"Gil","sequence":"additional","affiliation":[]},{"given":"Carles","family":"Bo","sequence":"additional","affiliation":[]},{"given":"Tatiana Y.","family":"Shvareva","sequence":"additional","affiliation":[]},{"given":"May","family":"Nyman","sequence":"additional","affiliation":[]},{"given":"Alexandra","family":"Navrotsky","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2014,3,6]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1211285"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2010.01.014"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300343c"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1080\/07366290701634636"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35136f"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300159x"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.2138\/am-2003-0725"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1119758109"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1090259"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ie2002582"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201207609"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207609"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00101a004"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9770000648"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2004.11.002"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201200801"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1053175"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja104964x"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic3005536"},{"key":"e_1_2_6_23_2","doi-asserted-by":"crossref","unstructured":"P. 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