{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,13]],"date-time":"2026-03-13T19:24:18Z","timestamp":1773429858427,"version":"3.50.1"},"reference-count":84,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2024,11,2]],"date-time":"2024-11-02T00:00:00Z","timestamp":1730505600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["Sche 384\/42-1"],"award-info":[{"award-number":["Sche 384\/42-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["SMAC - SUPRALUM"],"award-info":[{"award-number":["SMAC - SUPRALUM"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,1,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A new luminescent Cu(I) tetrametallic metallacycle <jats:bold>B<\/jats:bold> is reported that features very rare semi\u2010bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post\u2010synthetic transformation in the solid\u2010state, affording the new luminescent metallacycle <jats:bold>C<\/jats:bold>. Thermogravimetric analysis, IR spectroscopy and single\u2010crystal X\u2010ray diffraction reveal that this alteration preserves the gross tetrametallic macrocycle structure, but is caused by the release of the coordinated water molecules with the concomitant formation of cuprophilic interactions. This transition induces a shift from eye\u2010perceived green (<jats:bold>B<\/jats:bold>) to blue (<jats:bold>C<\/jats:bold>) room\u2010temperature luminescence for these molecular solids. Photophysical measurements and time\u2010dependent density\u2010functional theory calculations have been conducted to identify the origins of the emission properties lying in these structurally related assemblies, and suggest that thermally activated delayed fluorescence dominates the radiative relaxation pathways. This study highlights the innovative feature of Cu(I) derivatives, offering access to stimuli\u2010sensitive materials that can witness, a posteriori, the exceeding of critical temperatures in their environment.<\/jats:p>","DOI":"10.1002\/anie.202413151","type":"journal-article","created":{"date-parts":[[2024,9,19]],"date-time":"2024-09-19T12:55:21Z","timestamp":1726750521000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["High\u2010Temperature Solid\u2010State Post\u2010Synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5215-8908","authenticated-orcid":false,"given":"Adrien","family":"Schlachter","sequence":"first","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chendong","family":"Xu","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jana","family":"Schiller","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  D-93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Raquel Utrera","family":"Melero","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"S\u00e9bastien","family":"Kerneis","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2133-7214","authenticated-orcid":false,"given":"Guillaume","family":"Calvez","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0338-0494","authenticated-orcid":false,"given":"Karine","family":"Costuas","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2182-5020","authenticated-orcid":false,"given":"Manfred","family":"Scheer","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry University of Regensburg  D-93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6826-6409","authenticated-orcid":false,"given":"Christophe","family":"Lescop","sequence":"additional","affiliation":[{"name":"University of Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)  UMR 6226 F-35000 Rennes France"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,11,2]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.3c02887"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-023-00536-4"},{"key":"e_1_2_8_4_1","unstructured":"\u00a0"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201807768"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201807768"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aav2865"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201916379"},{"key":"e_1_2_8_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201916379"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT00192A"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2021.214176"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202103037"},{"key":"e_1_2_8_10_3","first-page":"12685","volume":"133","year":"2020","journal-title":"Angew. Chem."},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC01316E"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.1c01531"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.2c03322"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2022.214975"},{"key":"e_1_2_8_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202301000"},{"key":"e_1_2_8_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202301000"},{"key":"e_1_2_8_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3QI01739G"},{"key":"e_1_2_8_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsmaterialslett.4c00686"},{"key":"e_1_2_8_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3QI02466K"},{"key":"e_1_2_8_19_2","volume":"2400347","author":"Schlachter A.","year":"2024","journal-title":"Adv. Opt. Mater."},{"key":"e_1_2_8_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1DT01827B"},{"key":"e_1_2_8_21_1","unstructured":"\u00a0"},{"key":"e_1_2_8_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527691722"},{"key":"e_1_2_8_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2011.01.042"},{"key":"e_1_2_8_24_1","unstructured":"Nummerierung?"},{"key":"e_1_2_8_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.0c02683"},{"key":"e_1_2_8_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2017.09.011"},{"key":"e_1_2_8_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.4c00069"},{"key":"e_1_2_8_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c09458"},{"key":"e_1_2_8_29_2","author":"Tan Y.","year":"2024","journal-title":"Chem. Sci."},{"key":"e_1_2_8_30_1","unstructured":"\u00a0"},{"key":"e_1_2_8_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202000526"},{"key":"e_1_2_8_32_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.200874"},{"key":"e_1_2_8_33_1","unstructured":"\u00a0"},{"key":"e_1_2_8_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00074"},{"key":"e_1_2_8_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.202000144"},{"key":"e_1_2_8_36_1","unstructured":"\u00a0"},{"key":"e_1_2_8_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b06901"},{"key":"e_1_2_8_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1QI00937K"},{"key":"e_1_2_8_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202104497"},{"key":"e_1_2_8_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3QI01544K"},{"key":"e_1_2_8_41_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9QI01595G"},{"key":"e_1_2_8_42_1","unstructured":"\u00a0"},{"key":"e_1_2_8_43_2","unstructured":"For experimental details and characterization detailed photophysical and TGA-DTA measurements crystallographic data and computational details see ESI;"},{"key":"e_1_2_8_44_2","unstructured":"This exothermic event is the result of two concomitant processes (vide infra) : the de-coordination of the water molecule from the Cu(I) dimer that is expected to yield an exothermic event and the desorption of the released water molecules in an endothermic process. Very likely the exothermic contribution dominates."},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201900332"},{"key":"e_1_2_8_46_1","unstructured":"The remaining BF4\u2212counter-anions are located within the cavities lying between the metallacycles and don't share specific intermolecular interactions."},{"key":"e_1_2_8_47_1","unstructured":"\u00a0"},{"key":"e_1_2_8_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b02578"},{"key":"e_1_2_8_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/b105443k"},{"key":"e_1_2_8_50_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01035827"},{"key":"e_1_2_8_51_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0QI00691B"},{"key":"e_1_2_8_52_1","unstructured":"\u00a0"},{"key":"e_1_2_8_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700145r"},{"key":"e_1_2_8_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b00527"},{"key":"e_1_2_8_55_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC06098E"},{"key":"e_1_2_8_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.cgd.4c00614"},{"key":"e_1_2_8_57_1","unstructured":"The ground states are presenting Ci symmetry considering a maximum deviation of 0.5\u2009%. The symmetry was not imposed to allow a full geometry relaxation."},{"key":"e_1_2_8_58_1","unstructured":"C. Lescop Polym\u00e8re de coordination d'un pr\u00e9curseur \u00e0 base d'ions Cu(I) avec un ligand connecteur polytopique pr\u00e9sentant au moins une transition thermochrome irr\u00e9versible proc\u00e9d\u00e9 de fabrication et utilisations correspondants EP3820929 2020."},{"key":"e_1_2_8_59_1","first-page":"307","volume-title":"Methods in Enzymology","author":"Otwinowski Z.","year":"1997"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889898007717"},{"key":"e_1_2_8_61_1","volume-title":"SHELX97","author":"Sheldrick G. M.","year":"1997"},{"key":"e_1_2_8_62_1","unstructured":"\u00a0"},{"key":"e_1_2_8_63_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889802022112"},{"key":"e_1_2_8_64_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767389011189"},{"key":"e_1_2_8_65_1","unstructured":"\u00a0"},{"key":"e_1_2_8_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.81"},{"key":"e_1_2_8_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1606"},{"key":"e_1_2_8_68_1","unstructured":"\u00a0"},{"key":"e_1_2_8_69_2","first-page":"155","volume-title":", Recent Advances in Density Functional Methods, WORLD SCIENTIFIC","author":"Casida M. E."},{"key":"e_1_2_8_70_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-74626-0_12"},{"key":"e_1_2_8_71_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.78.382"},{"key":"e_1_2_8_72_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_2_8_73_1","unstructured":"\u00a0"},{"key":"e_1_2_8_74_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.472933"},{"key":"e_1_2_8_75_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.478522"},{"key":"e_1_2_8_76_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.463096"},{"key":"e_1_2_8_77_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.467146"},{"key":"e_1_2_8_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct800047t"},{"key":"e_1_2_8_79_1","unstructured":"R. Dennington T. Keith J. Millam GaussView (version 6.1) Semichem Inc Shawnee Mission KS2016."},{"key":"e_1_2_8_80_1","unstructured":"Deposition Numbers2368140(forB) 2368141 (forC) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202413151","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,5,15]],"date-time":"2025-05-15T08:11:28Z","timestamp":1747296688000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202413151"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,11,2]]},"references-count":84,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2025,1,2]]}},"alternative-id":["10.1002\/anie.202413151"],"URL":"https:\/\/doi.org\/10.1002\/anie.202413151","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,11,2]]},"assertion":[{"value":"2024-07-12","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-11-02","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202413151"}}