{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,10]],"date-time":"2026-02-10T08:41:36Z","timestamp":1770712896330,"version":"3.49.0"},"reference-count":84,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2022,5,20]],"date-time":"2022-05-20T00:00:00Z","timestamp":1653004800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2022,7,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The so\u2010called \u2018iron maiden\u2019 molecules belong to one of the most interesting subgroups of cyclophanes due to the presence of the ultrashort interaction between the C\uf8ffX apical bond and the benzene ring. This article presents an in\u2010depth theoretical study of 16 \u2018iron maiden\u2019 molecules, in which X\u00a0=\u00a0H, F, Cl or Br and the side chains are of various lengths and types: CSC, CSCC, CCC, and CCCC. It is shown that the H\u2009\u2192\u2009F\u2009\u2192\u2009Cl\u2009\u2192\u2009Br substitution leads to a significant expansion of the \u2018iron maiden\u2019 molecule. Shorter chains lead to more pronounced effects, while insertion of sulfur atoms into the side chains lowers them. Structural changes are associated with an increase in energetic destabilization of X. Moreover, unlike for H, in the case of X\u00a0=\u00a0halogen, the<jats:italic>out<\/jats:italic>\u2009\u2192\u2009<jats:italic>in<\/jats:italic>isomerization is energetically disadvantageous. The \u2018iron maiden\u2019 molecules are characterized by the presence of only three X\u22efC<jats:sub>Ar<\/jats:sub>bond paths. Particularly noteworthy are unusually large (even up to 32) values of the X\u22efC<jats:sub>Ar<\/jats:sub>bond ellipticity, which results from flat electron density distribution. The X\u22ef<jats:italic>\u03c0<\/jats:italic>interaction in each of the investigated \u2018iron maiden\u2019 molecule turned out to be multi\u2010center, stabilizing and almost purely covalent in nature as indicated by the definitely dominant percentage (94.8%\u2013101.6%) of the exchange\u2010correlation energy. The spatial hindrance within the \u2018iron maiden\u2019 molecules appears to be not so much due to the X\u22ef<jats:italic>\u03c0<\/jats:italic>repulsion, but due to unfavorable steric interactions between X and the C\uf8ffC side bonds. It is also confirmed that some CH\u22efHC interactions in aliphatic chains can be very weakly stabilizing.<\/jats:p>","DOI":"10.1002\/jcc.26879","type":"journal-article","created":{"date-parts":[[2022,5,20]],"date-time":"2022-05-20T13:30:49Z","timestamp":1653053449000},"page":"1206-1220","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["The physical nature of the ultrashort spike\u2013ring interaction in iron maiden molecules"],"prefix":"10.1002","volume":"43","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6455-051X","authenticated-orcid":false,"given":"Miros\u0142aw","family":"Jab\u0142o\u0144ski","sequence":"first","affiliation":[{"name":"Faculty of Chemistry Nicolaus Copernicus University in Toru\u0144 Toru\u0144 Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2022,5,20]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527603964"},{"key":"e_1_2_6_3_1","first-page":"2004","volume":"3763","author":"Pascal R. 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