The halogen bond to ethers - prototypic molecules and experimental electron density

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dc.contributor.authorSchmidt, Annika
dc.contributor.authorKrupp, Anna
dc.contributor.authorKleinheider, Johannes
dc.contributor.authorBinnenbrinkmann, Tamara M. L.
dc.contributor.authorWang, Ruimin
dc.contributor.authorEnglert, Ulli
dc.contributor.authorStrohmann, Carsten
dc.date.accessioned2024-09-04T08:09:38Z
dc.date.available2024-09-04T08:09:38Z
dc.date.issued2024-08-05
dc.description.abstractHalogen bonds to dialkyl ether molecules have remained largely unexplored. We here address the synthesis and the structural chemistry of the first halogen-bonded noncyclic alkyl ethers, combining 1,4-diiodotetrafluorobenzene and the prototypic or commonly used ethers dimethyl ether, tetrahydrofuran, and methyl-tert-butyl ether as halogen acceptors. Two different structural motifs based on moderately strong halogen bonds were obtained: Discrete trimolecular aggregates are formed, and unexpected halogen-bonded supramolecular chain adducts feature oxygen-bifurcated halogen bonds with 1:1 donor:acceptor ratio. Both structure types may be selectively obtained even for the same ether by adjusting the stoichiometry in the crystallization experiments. The geometric features of the etheric oxygen center were found to be flexible, in contrast to the almost linear geometry about the halogen donor atom. A high-resolution X-ray diffraction experiment on the extended adduct of dimethyl ether allowed us to study the electronic details of the acceptor-bifurcated I···O···I halogen bonds. The electron density in the bond critical points and derived properties such as the Laplacian indicate essentially electrostatic interactions and explain the geometrical flexibility of ethers in halogen bonds. Our studies demonstrate the great versatility of ethers as halogen bond acceptors, that can occur in many geometrical arrangements and whose contribution to nature’s structural designs should not be underestimated.en
dc.identifier.urihttp://hdl.handle.net/2003/42667
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-24503
dc.language.isoende
dc.relation.ispartofseriesACS omega;9(32)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subject.ddc540
dc.titleThe halogen bond to ethers - prototypic molecules and experimental electron densityen
dc.typeTexten
dc.type.publicationtypeArticleen
dcterms.accessRightsopen access
eldorado.secondarypublicationtrue
eldorado.secondarypublication.primarycitationSchmidt, A. et al. (2024) ‘The halogen bond to ethers - prototypic molecules and experimental electron density’, ACS omega, 9(32), pp. 35037–35045. Available at: https://doi.org/10.1021/acsomega.4c05124en
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1021/acsomega.4c05124

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