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Blue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density

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cris.lastimport.scopus2024-02-12T20:04:43Z
dc.abstract.enTriptycene derivatives are widely utilized in different fields of chemistry and materials sciences. Their physicochemical properties, often of pivotal importance for the rational design of triptycene-based functional materials, are influenced by noncovalent interactions between substituents mounted on the triptycene skeleton. Herein, a unique interaction between electron-rich substituents in the peri position and the silyl group located on the bridgehead sp(3)-carbon is discussed on the example of 1,4-dichloro-9-(p-methoxyphenyl)-silyltriptycene (TRPCl) which exists in solution in the form of two rotamers differing by dispositions, syn or anti, of the Si-C-Ph (the C-Ph atom is from the p-methoxyphenyl group) bond against the peri-Cl atom. For the first time, substantial differences between the Si-C-Ph bonds in these two dispositions are identified, based on indirect experimental and direct theoretical evidence. For these two orientations, the experimental (1)J(Si,C-Ph) values differ by as much as 10 percent. The differences are explained in terms of effective electron density transfer from the peri-Cl atom to the antibonding sigma* orbitals of the Si-X bonds (X=H, C-Ph) oriented anti to that atom. The electronic effects are revealed by an NBO analysis. Connections of these observations with the notion of blue-shifting hydrogen bonds are discussed.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorMAMES, Adam
dc.contributor.authorPietrzak, Mariusz
dc.contributor.authorKazimierczuk, Krzysztof
dc.contributor.authorSzymański, Sławomir
dc.contributor.authorRatajczyk, Tomasz
dc.contributor.authorGołowicz, Dariusz
dc.date.accessioned2024-01-24T18:40:11Z
dc.date.available2024-01-24T18:40:11Z
dc.date.issued2020
dc.description.financePublikacja bezkosztowa
dc.description.number6
dc.description.volume21
dc.identifier.doi10.1002/CPHC.201901141
dc.identifier.issn1439-4235
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/102390
dc.identifier.weblinkhttps://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cphc.201901141
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofChemPhysChem
dc.relation.pages540-545
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.subject.enblue-shift hydrogen bonds
dc.subject.enNMR spectroscopy
dc.subject.enquantum chemistry
dc.subject.enrotamers
dc.subject.entriptycene
dc.titleBlue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density
dc.typeJournalArticle
dspace.entity.typePublication