{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T01:02:04Z","timestamp":1790298124681,"version":"4.1.0"},"reference-count":60,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2020,4,29]],"date-time":"2020-04-29T00:00:00Z","timestamp":1588118400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000780","name":"European Commission","doi-asserted-by":"publisher","award":["ERCstg 802428"],"award-info":[{"award-number":["ERCstg 802428"]}],"id":[{"id":"10.13039\/501100000780","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["DE1830\/2-1"],"award-info":[{"award-number":["DE1830\/2-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPlusChem"],"published-print":{"date-parts":[[2020,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report on triethylene glycol\u2010based orthoformate cryptands, which adapt their bridgehead configurations in response to metal templates and intramolecular hydrogen bonding in a complex manner. In contrast to smaller <jats:bold>1.1.1<\/jats:bold>\u2010orthoformate cryptands, the inversion from <jats:italic><jats:bold>out,out<\/jats:bold><\/jats:italic><jats:bold>\u20102.2.2<\/jats:bold> to <jats:italic><jats:bold>in,in<\/jats:bold><\/jats:italic><jats:bold>\u20102.2.2<\/jats:bold> occurs spontaneously by thermal homeomorphic isomerization, i.\u2009e., without bond breakage. The global thermodynamic minimum of the entire network, which includes an unprecedented third isomer (<jats:italic><jats:bold>in,out<\/jats:bold><\/jats:italic><jats:bold>\u20102.2.2<\/jats:bold>), could only be reached under conditions that facilitate dynamic covalent exchange. Both inversion processes were studied in detail, including DFT calculations and MD simulations, which were particularly helpful for explaining differences between equilibrium compositions in solvents chloroform and acetonitrile. Unexpectedly, the system could be driven to the <jats:italic><jats:bold>in,out<\/jats:bold><\/jats:italic><jats:bold>\u20102.2.2<\/jats:bold> state by using a metal template with a size mismatch with respect to the <jats:italic><jats:bold>out,out<\/jats:bold><\/jats:italic><jats:bold>\u20102.2.2<\/jats:bold> cage.<\/jats:p>","DOI":"10.1002\/cplu.202000254","type":"journal-article","created":{"date-parts":[[2020,4,20]],"date-time":"2020-04-20T01:27:59Z","timestamp":1587346079000},"page":"1008-1012","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Self\u2010Assembly, Adaptive Response, and <i>in<\/i>,<i>out\u2010<\/i>Stereoisomerism of Large Orthoformate Cryptands"],"prefix":"10.1002","volume":"85","author":[{"given":"Henrik","family":"L\u00f6w","sequence":"first","affiliation":[{"name":"Institute of Organic Chemistry University of Ulm  Albert-Einstein-Allee 11 89081 Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elena","family":"Mena\u2010Osteritz","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry University of Ulm  Albert-Einstein-Allee 11 89081 Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kathleen M.","family":"Mullen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Physics Queensland University of Technology  Brisbane Queensland 4001 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1802-1892","authenticated-orcid":false,"given":"Christof M.","family":"J\u00e4ger","sequence":"additional","affiliation":[{"name":"Department of Chemical and Environmental Engineering University of Nottingham  University Park Nottingham NG7 2RD United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1852-2969","authenticated-orcid":false,"given":"Max","family":"von Delius","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry University of Ulm  Albert-Einstein-Allee 11 89081 Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,4,29]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC04598D"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940246k"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)81354-5"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01011a046"},{"key":"e_1_2_2_6_1","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200924g"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b12788"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201100893"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201100893"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/P19790002577"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00161a021"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199526601"},{"key":"e_1_2_2_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951072325"},{"key":"e_1_2_2_13_1","unstructured":"\u00a0"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20000818)39:16<2879::AID-ANIE2879>3.0.CO;2-J"},{"key":"e_1_2_2_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20000818)112:16<3001::AID-ANGE3001>3.0.CO;2-6"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198800891"},{"key":"e_1_2_2_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19881000110"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.190.4210.151"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01011a047"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/b009007g"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199618281"},{"key":"e_1_2_2_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19961081612"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00121a007"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00083c"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034972u"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200400058"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo801438d"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00410a009"},{"key":"e_1_2_2_26_1","unstructured":"\u00a0"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC05620A"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201800739"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00068a015"},{"key":"e_1_2_2_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC05968G"},{"key":"e_1_2_2_31_1","unstructured":"\u00a0"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020452p"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja402586c"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1367-5931(02)00331-9"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201600388"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3CS60356C"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3CS60336A"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3CS60342C"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar200240m"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.3390\/ijms160921858"},{"key":"e_1_2_2_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC03528C"},{"key":"e_1_2_2_42_1","unstructured":"\u00a0"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC01750F"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms8129"},{"key":"e_1_2_2_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201609855"},{"key":"e_1_2_2_45_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201609855"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b01350"},{"key":"e_1_2_2_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201903854"},{"key":"e_1_2_2_48_1","unstructured":"We 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