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The catalyst was bound in the cage by a ligand\u2010template approach, in which pyridyl\u2013zinc(II) porphyrin interactions led to high association constants (&gt;10<jats:sup>5<\/jats:sup>\u2009<jats:sc>m<\/jats:sc><jats:sup>\u22121<\/jats:sup>) for the binding of the ligands and the corresponding rhodium complex. DFT calculations confirm that the second coordination sphere forces the encapsulated active species to adopt the <jats:bold>ee<\/jats:bold> coordination geometry (i.e., both phosphine ligands in equatorial positions), in line with in situ high\u2010pressure IR studies of the host\u2013guest complex. The window aperture of the cage decreases slightly upon binding the catalyst. As a result, the diffusion of larger substrates into the cage is slower compared to that of smaller substrates. Consequently, the encapsulated rhodium catalyst displays substrate selectivity, converting smaller substrates faster to the corresponding aldehydes. This selectivity bears a resemblance to an effect observed in nature, where enzymes are able to discriminate between substrates based on shape and size by embedding the active site deep inside the hydrophobic pocket of a bulky protein structure.<\/jats:p>","DOI":"10.1002\/chem.201804333","type":"journal-article","created":{"date-parts":[[2018,10,23]],"date-time":"2018-10-23T13:20:50Z","timestamp":1540300850000},"page":"609-620","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":71,"title":["Size\u2010Selective Hydroformylation by a Rhodium Catalyst Confined in a Supramolecular Cage"],"prefix":"10.1002","volume":"25","author":[{"given":"Sandra S.","family":"Nurttila","sequence":"first","affiliation":[{"name":"Van't Hoff Institute for Molecular Sciences University of Amsterdam  Science Park 904 1098 XH Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wolfgang","family":"Brenner","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cambridge  Lensfield Road CB2 1EW Cambridge UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jes\u00fas","family":"Mosquera","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cambridge  Lensfield Road CB2 1EW Cambridge UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaj M.","family":"van\u2005Vliet","sequence":"additional","affiliation":[{"name":"Van't Hoff Institute for Molecular Sciences University of Amsterdam  Science Park 904 1098 XH Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jonathan R.","family":"Nitschke","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Cambridge  Lensfield Road CB2 1EW Cambridge UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5024-508X","authenticated-orcid":false,"given":"Joost N. 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