{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,4]],"date-time":"2026-04-04T10:59:07Z","timestamp":1775300347631,"version":"3.50.1"},"reference-count":39,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2022,3,11]],"date-time":"2022-03-11T00:00:00Z","timestamp":1646956800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m\u2032-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m\u2032-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement\u2014t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH\u2014were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo\u2013phenol\u21c4quinone\u2013hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. 1H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH.<\/jats:p>","DOI":"10.3390\/molecules27061835","type":"journal-article","created":{"date-parts":[[2022,3,13]],"date-time":"2022-03-13T22:29:43Z","timestamp":1647210583000},"page":"1835","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2548-3454","authenticated-orcid":false,"given":"Ewa","family":"Wagner-Wysiecka","sequence":"first","affiliation":[{"name":"Department of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paulina","family":"Szulc","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"El\u017cbieta","family":"Luboch","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2453-8214","authenticated-orcid":false,"given":"Jaros\u0142aw","family":"Chojnacki","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Pawe\u0142","family":"Sowi\u0144ski","sequence":"additional","affiliation":[{"name":"Nuclear Magnetic Resonance Laboratory, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Katarzyna","family":"Szwarc-Karabyka","sequence":"additional","affiliation":[{"name":"Nuclear Magnetic Resonance Laboratory, Faculty of Chemistry, Gda\u0144sk University of Technology, Narutowicza Street 11\/12, 80-233 Gda\u0144sk, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,3,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1557","DOI":"10.1016\/j.matt.2020.09.019","article-title":"Versatile roles of macrocycles in organic-inorganic hybrid materials for biomedical applications","volume":"3","author":"Yue","year":"2020","journal-title":"Matter"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2653","DOI":"10.1007\/s11164-021-04432-8","article-title":"Synthesis of new chiral macrocycles-based glycolipids and its application in asymmetric Michael addition","volume":"47","author":"Sabah","year":"2021","journal-title":"Res. 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