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Donor ligands such as phosphanes can stabilize the resulting <jats:bold>[LCu<jats:sub>4<\/jats:sub>]<\/jats:bold> units, which then remain monomeric (<jats:bold>[(Ph<jats:sub>3<\/jats:sub>PCu)<jats:sub>4<\/jats:sub>L]<\/jats:bold>). In the absence of donor ligands, they aggregate, providing a hexamer (<jats:bold>[LCu<jats:sub>4<\/jats:sub>]<jats:sub>6<\/jats:sub><\/jats:bold>) in high yields, with a hollow\u2010sphere structure formed by an unprecedented Cu<jats:sub>24<\/jats:sub>S<jats:sub>48<\/jats:sub> cage that is surrounded by the organic framework of the calixarene chalices. Preliminary NMR experiments with regard to the host\u2010guest chemistry in solution showed that the compound represents a polytopic host for acetonitrile and methane.<\/jats:p>","DOI":"10.1002\/anie.201915882","type":"journal-article","created":{"date-parts":[[2020,2,3]],"date-time":"2020-02-03T09:15:43Z","timestamp":1580721343000},"page":"6735-6739","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":24,"title":["Mercaptothiacalixarenes Steer 24 Copper(I) Centers to form a Hollow\u2010Sphere Structure Featuring Cu<sub>2<\/sub>S<sub>2<\/sub> Motifs with Exceptionally Short Cu\u22c5\u22c5\u22c5Cu Distances"],"prefix":"10.1002","volume":"59","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0448-3092","authenticated-orcid":false,"given":"Nicolas","family":"Frank","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0141-2635","authenticated-orcid":false,"given":"Andr\u00e9","family":"Dallmann","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6262-4925","authenticated-orcid":false,"given":"Beatrice","family":"Braun\u2010Cula","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christian","family":"Herwig","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0751-1386","authenticated-orcid":false,"given":"Christian","family":"Limberg","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Stra\u00dfe 2 12489 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2020,3,3]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19990104)5:1<19::AID-CHEM19>3.0.CO;2-7"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(01)47012-2"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700354"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c4cs00068d"},{"key":"e_1_2_2_6_1","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/a906058h"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1472-7862(02)00069-2"},{"key":"e_1_2_2_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/b502999f"},{"key":"e_1_2_2_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/b201379g"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/B816066J"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020620d"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2005.06.013"},{"key":"e_1_2_2_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201901411"},{"key":"e_1_2_2_15_1","unstructured":"\u00a0"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2014.06.011"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.1600323"},{"key":"e_1_2_2_18_1","unstructured":"\u00a0"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35252D"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)84307-7"},{"key":"e_1_2_2_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC08301C"},{"key":"e_1_2_2_22_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2052520616003954"},{"key":"e_1_2_2_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja970513e"},{"key":"e_1_2_2_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100785a001"},{"key":"e_1_2_2_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19980615)4:6<1016::AID-CHEM1016>3.0.CO;2-B"},{"key":"e_1_2_2_26_1","doi-asserted-by":"publisher","DOI":"10.1080\/10610270701747057"},{"key":"e_1_2_2_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.04.050"},{"key":"e_1_2_2_28_1","unstructured":"CCDC\u20051970789 and 1970788contain the supplementary crystallographic data for this paper. 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