{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,15]],"date-time":"2026-05-15T12:20:02Z","timestamp":1778847602342,"version":"3.51.4"},"reference-count":37,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2008,1,30]],"date-time":"2008-01-30T00:00:00Z","timestamp":1201651200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Magnetic Reson in Chemistry"],"published-print":{"date-parts":[[2008,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Interaction of H<jats:sub>3<\/jats:sub>O<jats:sup>+<\/jats:sup> or H<jats:sub>5<\/jats:sub>O<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> with 1,3\u2010alternate tetrapropoxycalix[4]arene (1) was studied in nitrobenzene and dichloromethane using <jats:sup>1<\/jats:sup>H and <jats:sup>13<\/jats:sup>C NMR including transverse and rotating\u2010frame relaxations and density functional level of theory (DFT) quantum calculations. According to NMR, the ion forms an equimolecular complex with 1 with the equilibrium constant <jats:italic>K<\/jats:italic> being 3.97 \u00d7 10<jats:sup>3<\/jats:sup> L.mol<jats:sup>\u22121<\/jats:sup> at 296 K. The ions are bound by strong hydrogen bonds to the phenoxy\u2010oxygen atoms of one half of 1 and by a medium\u2010strong hydrogen bond to the \u03c0 system of the aromatic rings of the other half. The complex appears to have C<jats:sub>4h<\/jats:sub> symmetry in NMR even when cooling its solution down to 213 K, which could be due either to a genuine symmetry of the complex (if the ion is H<jats:sub>5<\/jats:sub>O<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup>) or to fast structure averaging by ion exchange processes (if the ion is H<jats:sub>3<\/jats:sub>O<jats:sup>+<\/jats:sup>). Therefore, the dynamics of the system was studied. Using two independent NMR methods (transverse and rotating\u2010frame relaxation), two different exchange processes were discerned with correlation times 25 \u00d7 10<jats:sup>\u22126<\/jats:sup> and 5 \u00d7 10<jats:sup>\u22126<\/jats:sup> s, the first being clearly intermolecular and the other being apparently intramolecular. The energetic aspects of the possible exchange processes were examined by DFT quantum calculations. Rotation of H<jats:sub>3<\/jats:sub>O<jats:sup>+<\/jats:sup> ion within one binding site with the energy barrier 8.13 kcal\/mol is easily possible. Intermolecular exchange by freeing the ion from the complex has too high a barrier but cooperative interaction of the ion with additional water molecules makes it viable. The intramolecular exchange (or hopping) of the H<jats:sub>3<\/jats:sub>O<jats:sup>+<\/jats:sup> ion between the two sites of the molecule is not viable in the classical manner, the barrier being 25.6 kcal\/mol. Quantum tunneling of the ion is highly improbable, too. Alternative mechanisms including concerted two\u2010ion intermolecular exchange and cooperative interaction with another bound water molecule including complexation with proton dihydrate H<jats:sub>5<\/jats:sub>O<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> are discussed. Copyright \u00a9 2008 John Wiley &amp; Sons, Ltd.<\/jats:p>","DOI":"10.1002\/mrc.2169","type":"journal-article","created":{"date-parts":[[2008,1,30]],"date-time":"2008-01-30T12:20:20Z","timestamp":1201695620000},"page":"235-243","source":"Crossref","is-referenced-by-count":12,"title":["Cooperative interaction of H<sub>3<\/sub>O<sup>+<\/sup> with 1,3\u2010alternate tetrapropoxycalix[4]arene: NMR and theoretical study"],"prefix":"10.1002","volume":"46","author":[{"given":"Jaroslav","family":"K\u0159\u00ed\u017e","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ji\u0159\u00ed","family":"Dybal","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Emanuel","family":"Makrl\u00edk","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jan","family":"Budka","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,1,30]]},"reference":[{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/9781847550293"},{"key":"e_1_2_1_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199507131"},{"key":"e_1_2_1_4_2","doi-asserted-by":"publisher","DOI":"10.1142\/p168"},{"key":"e_1_2_1_5_2","doi-asserted-by":"publisher","DOI":"10.1007\/0-306-47522-7"},{"key":"e_1_2_1_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)87626-2"},{"key":"e_1_2_1_7_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00663045"},{"key":"e_1_2_1_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00205a018"},{"key":"e_1_2_1_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00064a013"},{"key":"e_1_2_1_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0003-2670(96)00555-7"},{"key":"e_1_2_1_11_2","doi-asserted-by":"publisher","DOI":"10.1080\/00958970108027147"},{"key":"e_1_2_1_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja020764"},{"key":"e_1_2_1_13_2","doi-asserted-by":"publisher","DOI":"10.1023\/A:1016083624362"},{"key":"e_1_2_1_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/b401423p"},{"key":"e_1_2_1_15_2","first-page":"3","volume":"28","author":"Gutsche CD","year":"1995","journal-title":"Aldrichim. 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