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  Intramolecular London Dispersion Interaction Effects on Gas-Phase and Solid-State Structures of Diamondoid Dimers

Fokin, A. A., Zhuk, T. S., Blomeyer, S., Pérez, C., Chernish, L. V., Pashenko, A. E., et al. (2017). Intramolecular London Dispersion Interaction Effects on Gas-Phase and Solid-State Structures of Diamondoid Dimers. Journal of the American Chemical Society, 139(46), 16696-16707. doi:10.1021/jacs.7b07884.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0001-F591-6 Version Permalink: http://hdl.handle.net/21.11116/0000-0001-F592-5
Genre: Journal Article

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https://dx.doi.org/10.1021/jacs.7b07884 (Publisher version)
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 Creators:
Fokin, A. A.1, 2, Author
Zhuk, T. S.1, Author
Blomeyer, S.3, Author
Pérez, C.4, Author              
Chernish, L. V.1, Author
Pashenko, A. E.1, Author
Antony, J.5, Author
Vishnevskiy, Y. V.3, Author
Berger, R. J. F.6, Author
Grimme, S.5, Author
Logemann, C.7, Author
Schnell, M.4, Author              
Mitzel, N. W.3, Author
Schreiner, P. R.2, Author
Affiliations:
1Department of Organic Chemistry, Igor Sikorsky Kiev Polytechnic Institute, ou_persistent22              
2Institute of Organic Chemistry, Justus-Liebig University, ou_persistent22              
3Lehrstuhl für Anorganische Chemie und Strukturchemie, Universität Bielefeld, ou_persistent22              
4Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938292              
5Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, ou_persistent22              
6Materialchemie, Paris-Lodron Universität Salzburg, ou_persistent22              
7Institute of Inorganic and Analytical Chemistry, Justus-Liebig University, ou_persistent22              

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 Abstract: The covalent diamantyl (C28H38) and oxadiamantyl (C26H34O2) dimers are stabilized by London dispersion attractions between the dimer moieties. Their solid-state and gas-phase structures were studied using a multitechnique approach, including single-crystal X-ray diffraction (XRD), gas-phase electron diffraction (GED), a combined GED/microwave (MW) spectroscopy study, and quantum chemical calculations. The inclusion of medium-range electron correlation as well as the London dispersion energy in density functional theory is essential to reproduce the experimental geometries. The conformational dynamics computed for C26H34O2 agree well with solution NMR data and help in the assignment of the gas-phase MW data to individual diastereomers. Both in the solid state and the gas phase the central C–C bond is of similar length for the diamantyl [XRD, 1.642(2) Å; GED, 1.630(5) Å] and the oxadiamantyl dimers [XRD, 1.643(1) Å; GED, 1.632(9) Å; GED+MW, 1.632(5) Å], despite the presence of two oxygen atoms. Out of a larger series of quantum chemical computations, the best match with the experimental reference data is achieved with the PBEh-3c, PBE0-D3, PBE0, B3PW91-D3, and M06-2X approaches. This is the first gas-phase confirmation that the markedly elongated C–C bond is an intrinsic feature of the molecule and that crystal packing effects have only a minor influence.

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Language(s): eng - English
 Dates: 2017-08-102017-11-172017-11-22
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jacs.7b07884
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 139 (46) Sequence Number: - Start / End Page: 16696 - 16707 Identifier: ISSN: 0002-7863
CoNE: /journals/resource/954925376870