Density Functional Theory Calculations of Hydrogen-Bond-Mediated NMR J Coupling in the Solid State.
Abstract: A recently developed method for calculating NMR J coupling in solid-state systems is applied to calculate hydrogen-bond-mediated J couplings across intra- or intermolecular N-H∙∙∙N hydrogen bonds in two 6-aminofulvene-1-aldimine derivatives and the ribbon structure formed by a deoxyguanosi...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 38; pp. 12663 - 12671 |
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| Autores principales: | , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
9/24/2008
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=34491666&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 34491666 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 9/24/2008 vid: 130 iid: 38 pid: 997 pub: American Chemical Society artinfo: ui: 34491666 10.1021/ja800419m ppf: 12663 ppct: 8 formats: tig: atl: Density Functional Theory Calculations of Hydrogen-Bond-Mediated NMR J Coupling in the Solid State. aug: au: Joyce, Siân A. Yates, Jonathan R. Pickard, Chris J. Brown, Steven P. affil: Tyndall National institute, Lee Maltings, Prospect Row, Cork, Ireland TCM Group, Cavendish Laboratory, University of Cambridge, 19 J. J. Thomson Avenue, Cambridge CB3 OHE, U.K. School of Physics and Astronomy, University of St. Andrews, North Haugh, St. Andrews KY16 9SS, U.K. Department of Physics, University of Warwick, Coventry CV4 7AL, U.K. su: Density functionals Hydrogen bonding Solid state chemistry Nuclear magnetic resonance spectroscopy Crystal lattices Electrostatics Intermolecular forces sug: subj: Density functionals Hydrogen bonding Solid state chemistry Nuclear magnetic resonance spectroscopy Crystal lattices Electrostatics Intermolecular forces ab: Abstract: A recently developed method for calculating NMR J coupling in solid-state systems is applied to calculate hydrogen-bond-mediated J couplings across intra- or intermolecular N-H∙∙∙N hydrogen bonds in two 6-aminofulvene-1-aldimine derivatives and the ribbon structure formed by a deoxyguanosine derivative. Excellent quantitative agreement is observed between the calculated solid-state J couplings and those previously determined experimentally in two recent spin-echo magic-angle-spinning NMR studies (Brown, S. P.; et al. Chem. Commun.2002, 1852-1853 and Pham, T. N.; et al. Phys. Chem. Chem. Phys. 2007, 9, 3416-3423). For the 6-aminofulvene-1 -aldimines, the differences in 2hJNN couplings in pyrrole and triazole derivatives are reproduced, while for the guanosine ribbons, an increase in 2hJNN is correlated with a decrease in the N-H∙∙∙N hydrogen-bond distance. Jcouplings are additionally calculated for isolated molecules of the 6-aminofulevene-1 -aldimines extracted from the crystal with and without further geometry optimization. Importantly, it is shown that experimentally observed differences between J couplings determined by solution- and solid-state NMR are not solely due to differences in geometry; long-range electrostatic effects of the crystal lattice are shown to be significant also. J couplings that are yet to be experimentally measured are calculated. Notably, J couplings across N-H∙∙∙N hydrogen bonds are found to be of a similar magnitude to J couplings, suggesting that their utilization and quantitative determination should be experimentally feasible. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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