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231226s2022 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.26879
|2 doi
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|a pubmed24n1137.xml
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|a (DE-627)NLM341163953
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|a (NLM)35593685
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|a DE-627
|b ger
|c DE-627
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|a eng
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|a Jabłoński, Mirosław
|e verfasserin
|4 aut
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|a The physical nature of the ultrashort spike-ring interaction in iron maiden molecules
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|c 2022
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|a Text
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|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|2 rdacarrier
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|a Date Completed 30.05.2022
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|a Date Revised 07.09.2022
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a © 2022 Wiley Periodicals LLC.
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|a The so-called 'iron maiden' molecules belong to one of the most interesting subgroups of cyclophanes due to the presence of the ultrashort interaction between the CX apical bond and the benzene ring. This article presents an in-depth theoretical study of 16 'iron maiden' molecules, in which X = H, 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 → F → Cl → Br substitution leads to a significant expansion of the 'iron maiden' 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 = halogen, the out → in isomerization is energetically disadvantageous. The 'iron maiden' molecules are characterized by the presence of only three X⋯CAr bond paths. Particularly noteworthy are unusually large (even up to 32) values of the X⋯CAr bond ellipticity, which results from flat electron density distribution. The X⋯π interaction in each of the investigated 'iron maiden' molecule turned out to be multi-center, stabilizing and almost purely covalent in nature as indicated by the definitely dominant percentage (94.8%-101.6%) of the exchange-correlation energy. The spatial hindrance within the 'iron maiden' molecules appears to be not so much due to the X⋯π repulsion, but due to unfavorable steric interactions between X and the CC side bonds. It is also confirmed that some CH⋯HC interactions in aliphatic chains can be very weakly stabilizing
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|a Journal Article
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|a bond ellipticity
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|a covalence
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|a cyclophane
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|a exchange-correlation energy
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|a halogen
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|a iron maiden
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|a multi-center interaction
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|a repulsion
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|a steric crowding
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|a total delocalization index
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|a Halogens
|2 NLM
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|a Iron
|2 NLM
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|a E1UOL152H7
|2 NLM
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 43(2022), 18 vom: 05. Juli, Seite 1206-1220
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:43
|g year:2022
|g number:18
|g day:05
|g month:07
|g pages:1206-1220
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|u http://dx.doi.org/10.1002/jcc.26879
|3 Volltext
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