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From the analysis of the rotational parameters of the parent species and of the <jats:sup>13<\/jats:sup>C and <jats:sup>15<\/jats:sup>N isotopologues, the structural arrangement of the adduct has been unambiguously established. The full ring fluorination of pyridine has a dramatic effect on its binding properties: It alters the electron density distribution at the \u03c0\u2010cloud of pyridine creating a \u03c0\u2010hole and changing its electron donor\u2010acceptor capabilities. In the complex, formaldehyde lies above the aromatic ring with one of the oxygen lone pairs, as conventionally envisaged, pointing toward its centre. This lone pair\u22c5\u22c5\u22c5\u03c0\u2010hole interaction, reinforced by a weak C\u2212H\u22c5\u22c5\u22c5N interaction, indicates an exchange of the electron\u2010acceptor roles of both molecules when compared to the pyridine\u22c5\u22c5\u22c5formaldehyde adduct. Tunnelling doublets due to the internal rotation of formaldehyde have also been observed and analysed leading to a discussion on the competition between lone pair\u22c5\u22c5\u22c5\u03c0\u2010hole and \u03c0\u22c5\u22c5\u22c5\u03c0 stacking interactions.<\/jats:p>","DOI":"10.1002\/chem.202102163","type":"journal-article","created":{"date-parts":[[2021,8,4]],"date-time":"2021-08-04T13:08:57Z","timestamp":1628082537000},"page":"13870-13878","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["How Aromatic Fluorination Exchanges the Interaction Role of Pyridine with Carbonyl Compounds: The Formaldehyde Adduct"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1028-779X","authenticated-orcid":false,"given":"Juan Carlos","family":"L\u00f3pez","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica y Qu\u00edmica Inorg\u00e1nica Facultad de Ciencias IU CINQUIMA Universidad de Valladolid  47011 Valladolid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3014-7674","authenticated-orcid":false,"given":"Alberto","family":"Macario","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica y Qu\u00edmica Inorg\u00e1nica Facultad de Ciencias IU CINQUIMA Universidad de Valladolid  47011 Valladolid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2644-0023","authenticated-orcid":false,"given":"Assimo","family":"Maris","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica \u201cG. 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