Journal article

Publication year: 2017

Pages: 16696-16707

Journal: Journal of the American Chemical Society

Volume number: 139

Issue number: 46

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/jacs.7b07884

Publisher: American Chemical Society

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.

Harvard Citation style: Fokin, A., Zhuk, T., Blomeyer, S., Perez, C., Chernish, L., Pashenko, A., 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), pp. 16696-16707. https://doi.org/10.1021/jacs.7b07884

APA Citation style: Fokin, A., Zhuk, T., Blomeyer, S., Perez, C., Chernish, L., Pashenko, A., Antony, J., Vishnevskiy, Y., Berger, R., Grimme, S., Logemann, C., Schnell, M., Mitzel, N., & Schreiner, P. (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. https://doi.org/10.1021/jacs.7b07884