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The crystal structure of these lanthanide silicates was solved from high\u2010resolution synchrotron power X\u2010ray diffraction data collected at 110\u2005K, and further supported by <jats:sup>29<\/jats:sup>Si MAS NMR and Eu<jats:sup>3+<\/jats:sup> luminescence. The materials crystallize in the <jats:italic>P<\/jats:italic>\u012b triclinic centrosymmetric space group, exhibiting a dense framework consisting of hexameric [Si<jats:sub>6<\/jats:sub>O<jats:sub>18<\/jats:sub>]<jats:sup>12\u2212<\/jats:sup> cyclosilicate units, and chains of two distinct {LnO<jats:sub>6<\/jats:sub>} octahedra. Na<jats:sub>2<\/jats:sub>K[(Lu<jats:sub>0.75<\/jats:sub>Yb<jats:sub>0.20<\/jats:sub>Er<jats:sub>0.05<\/jats:sub>)<jats:sub>3<\/jats:sub>Si<jats:sub>6<\/jats:sub>O<jats:sub>18<\/jats:sub>] is the first example of a lanthanide silicate operative as a near\u2010infrared ratiometric luminescent thermometer, with good sensitivity at cryogenic temperatures (&lt;100\u2005K). Upon excitation at 903\u2005nm, the ratio between the <jats:sup>2<\/jats:sup>F<jats:sub>7\/2<\/jats:sub>\u2192<jats:sup>2<\/jats:sup>F<jats:sub>5\/2<\/jats:sub> (Yb<jats:sup>3+<\/jats:sup>) and <jats:sup>4<\/jats:sup>I<jats:sub>13\/2<\/jats:sub>\u2192<jats:sup>4<\/jats:sup>I<jats:sub>15\/2<\/jats:sub> (Er<jats:sup>3+<\/jats:sup>) emissions was used for sensing temperature in the 12\u2013450\u2005K range, reaching a maximum thermal sensitivity of 2.6\u2009%\u2009K<jats:sup>\u22121<\/jats:sup> at 26.8\u2005K.<\/jats:p>","DOI":"10.1002\/chem.201802219","type":"journal-article","created":{"date-parts":[[2018,7,3]],"date-time":"2018-07-03T07:27:30Z","timestamp":1530602850000},"page":"11926-11935","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":37,"title":["Near\u2010Infrared Ratiometric Luminescent Thermometer Based on a New Lanthanide 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