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However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La<jats:sup>3+<\/jats:sup> and Nd<jats:sup>3+<\/jats:sup>) is explored in molten LiCl\u2010KCl\u2010LiF\u2010LnCl<jats:sub>3<\/jats:sub> salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln<jats:sup>3+<\/jats:sup> occur when F<jats:sup>\u2212<\/jats:sup> concentration increases, indicating that the F<jats:sup>\u2212<\/jats:sup> anions interact with Ln<jats:sup>3+<\/jats:sup> via substituting the coordinated Cl<jats:sup>\u2212<\/jats:sup> anions, and confirm [LnCl<jats:sub>x<\/jats:sub>F<jats:sub>y<\/jats:sub>]<jats:sup>3\u2212x\u2212y<\/jats:sup> (y<jats:sub>max<\/jats:sub>=3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl<jats:sup>\u2212<\/jats:sup> and F<jats:sup>\u2212<\/jats:sup> anions, which leads to the formation of four distinct Ln(III) species: [LnCl<jats:sub>6<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup>, [LnCl<jats:sub>5<\/jats:sub>F]<jats:sup>3\u2212<\/jats:sup>, [LnCl<jats:sub>4<\/jats:sub>F<jats:sub>2<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup> and [LnCl<jats:sub>4<\/jats:sub>F<jats:sub>3<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup>. Among them, the seven\u2010coordinated [LnCl<jats:sub>4<\/jats:sub>F<jats:sub>3<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup> complex possesses a low\u2010symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z\/r) among different metal cations, it was concluded that Ln\u2212F interaction is weaker than that between transition metal and F<jats:sup>\u2212<\/jats:sup> ions.<\/jats:p>","DOI":"10.1002\/chem.202101505","type":"journal-article","created":{"date-parts":[[2021,6,9]],"date-time":"2021-06-09T08:33:12Z","timestamp":1623227592000},"page":"11721-11729","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":43,"title":["Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La<sup>3+<\/sup> and Nd<sup>3+<\/sup>) in Molten Salts"],"prefix":"10.1002","volume":"27","author":[{"given":"Shilin","family":"Jiang","sequence":"first","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"},{"name":"University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianhui","family":"Lan","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin","family":"Wang","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yalan","family":"Liu","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuke","family":"Zhong","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"},{"name":"University of Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yichuan","family":"Liu","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liyong L.\u2010Y.","family":"Yuan","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lirong","family":"Zheng","sequence":"additional","affiliation":[{"name":"Beijing Synchrotron Radiation Facility Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhifang","family":"Chai","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"},{"name":"Engineering Laboratory of Advanced Energy Materials Ningbo Institute of Industrial Technology Chinese Academy of Sciences  Ningbo 315201 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9929-9732","authenticated-orcid":false,"given":"Weiqun","family":"Shi","sequence":"additional","affiliation":[{"name":"Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences  Beijing 100049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,7,5]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010297z"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1753928"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aau7628"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.333572"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1038\/35104634"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14438"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1179\/imr.1992.37.1.197"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","unstructured":"F. 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