{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,29]],"date-time":"2026-04-29T11:44:28Z","timestamp":1777463068844,"version":"3.51.4"},"reference-count":59,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2017,12,5]],"date-time":"2017-12-05T00:00:00Z","timestamp":1512432000000},"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>MP2\/aug-cc-pVTZ calculations were performed for complexes of BrF3 and BrF5 acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its \u03c3-bond, while in remaining moieties\u2014in complexes of hydrocarbons; such an electron transfer follows from \u03c0-electrons. The complexes are linked by a kind of the halogen bond that is analyzed for the first time in this study, i.e., it is the link between the multivalent halogen and \u03c0 or \u03c3-electrons. The nature of such a halogen bond is discussed, as well as various dependencies and correlations are presented. Different approaches are applied here, the Quantum Theory of Atoms in Molecules, Natural Bond Orbital method, the decomposition of the energy of interaction, the analysis of electrostatic potentials, etc.<\/jats:p>","DOI":"10.3390\/molecules22122150","type":"journal-article","created":{"date-parts":[[2017,12,5]],"date-time":"2017-12-05T11:50:28Z","timestamp":1512474628000},"page":"2150","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["New Type of Halogen Bond: Multivalent Halogen Interacting with \u03c0- and \u03c3-Electrons"],"prefix":"10.3390","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4161-2938","authenticated-orcid":false,"given":"S\u0142awomir","family":"Grabowski","sequence":"first","affiliation":[{"name":"Faculty of Chemistry, University of the Basque Country and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia, Spain"},{"name":"IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2017,12,5]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2511","DOI":"10.1002\/1521-3765(20010618)7:12<2511::AID-CHEM25110>3.0.CO;2-T","article-title":"Halogen Bonding: A Paradigm in Supramolecular Chemistry","volume":"7","author":"Metrangolo","year":"2001","journal-title":"Chem. 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