{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,16]],"date-time":"2025-10-16T00:34:34Z","timestamp":1760574874300,"version":"build-2065373602"},"reference-count":35,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2022,4,13]],"date-time":"2022-04-13T00:00:00Z","timestamp":1649808000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Org Chem"],"published-print":{"date-parts":[[2022,4,21]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Cadmium porphyrin cage compounds <jats:bold>Cd1<\/jats:bold> and <jats:sup><jats:bold>113<\/jats:bold><\/jats:sup><jats:bold>Cd1<\/jats:bold> have been synthesized from the free base porphyrin cage derivative <jats:bold>H<jats:sub>2<\/jats:sub>1<\/jats:bold> and Cd(OAc)<jats:sub>2<\/jats:sub>\u2009\u22c5\u20092 H<jats:sub>2<\/jats:sub>O or <jats:sup>113<\/jats:sup>Cd(OAc)<jats:sub>2<\/jats:sub>\u2009\u22c5\u20092 H<jats:sub>2<\/jats:sub>O, respectively. The compounds form allosteric complexes with the positively charged guests <jats:italic>N,N<\/jats:italic>\u2032\u2010dimethylimidazolium hexafluorophosphate (<jats:bold>DMI<\/jats:bold>) and <jats:italic>N,N<\/jats:italic>\u2032\u2010dimethylviologen dihexafluorophosphate (<jats:bold>Me<jats:sub>2<\/jats:sub>V<\/jats:bold>), which bind in the cavity of the cage, and <jats:bold>tbupy<\/jats:bold>, which coordinates as an axial ligand to the outside of the cage. In the presence of <jats:bold>tbupy<\/jats:bold>, the binding of <jats:bold>DMI<\/jats:bold> in <jats:bold>Cd1<\/jats:bold> is enhanced by a factor of \u223c31, while the presence of <jats:bold>DMI<\/jats:bold> or <jats:bold>Me<jats:sub>2<\/jats:sub>V<\/jats:bold> in the cavity of <jats:bold>Cd1<\/jats:bold> enhances the binding of <jats:bold>tbupy<\/jats:bold> by factors of 55 and 85, respectively. The X\u2010ray structures of the coordination complexes of <jats:bold>Cd1<\/jats:bold> with acetone, acetonitrile, and pyridine, the host\u2010guest complex of <jats:bold>Cd1<\/jats:bold> with a bound viologen guest, and the ternary allosteric complex of <jats:bold>Cd1<\/jats:bold> with a bound <jats:bold>DMI<\/jats:bold> guest and a coordinated <jats:bold>tbupy<\/jats:bold> ligand, were solved. These structures revealed relocations of the cadmium center in and out of the porphyrin plane, depending on whether a guest or a ligand is present. <jats:sup>113<\/jats:sup>Cd NMR could be employed as a tool to quantify the binding of guests and ligands to <jats:sup><jats:bold>113<\/jats:bold><\/jats:sup><jats:bold>Cd1<\/jats:bold>. 1D EXSY experiments on the ternary allosteric system <jats:bold>Cd1\u2010tbupy\u2010Me<jats:sub>2<\/jats:sub>V<\/jats:bold> revealed that the coordination of <jats:bold>tbupy<\/jats:bold> significantly slowed down the dissociation of the <jats:bold>Me<jats:sub>2<\/jats:sub>V<\/jats:bold> guest. Eyring plots of the dissociation process revealed that this kinetic allosteric effect is entropic in nature.<\/jats:p>","DOI":"10.1002\/ejoc.202200111","type":"journal-article","created":{"date-parts":[[2022,4,13]],"date-time":"2022-04-13T09:09:25Z","timestamp":1649840965000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["<sup>113<\/sup>Cd as a Probe in NMR Studies of Allosteric Host\u2010Guest\u2010Ligand Complexes of Porphyrin Cage Compounds"],"prefix":"10.1002","volume":"2022","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5020-1420","authenticated-orcid":false,"given":"Jeroen P. 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