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Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state
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Joyce, Sian A., Yates, Jonathan R., Pickard, Chris J. and Brown, Steven P. (2008) Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. Journal of the American Chemical Society, Vol.130 (No.38). pp. 12663-12670. doi:10.1021/ja800419m ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/ja800419m
Abstract
A recently developed method for calculating NMR J coupling in solid-state systems is applied to calculate hydrogen-bond-mediated (2h)J(NN) Couplings across intra- or intermolecular N-H center dot center dot center dot 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 (2h)J(NN) couplings in pyrrole and triazole derivatives are reproduced, while for the guanosine ribbons, an increase in (2h)J(NN) is correlated with a decrease in the N-H center dot center dot center dot N hydrogen-bond distance. J couplings 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, (2h)J(NO) couplings across N-H center dot center dot center dot O hydrogen bonds are found to be of a similar magnitude to (2h)J(NN) Couplings, suggesting that their utilization and quantitative determination should be experimentally feasible.
| Item Type: | Journal Article | ||||
|---|---|---|---|---|---|
| Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | ||||
| Library of Congress Subject Headings (LCSH): | Nuclear magnetic resonance, Electron spin echoes, Density functionals, Hydrogen bonding | ||||
| Journal or Publication Title: | Journal of the American Chemical Society | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 0002-7863 | ||||
| Official Date: | 24 September 2008 | ||||
| Dates: |
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| Volume: | Vol.130 | ||||
| Number: | No.38 | ||||
| Number of Pages: | 8 | ||||
| Page Range: | pp. 12663-12670 | ||||
| DOI: | 10.1021/ja800419m | ||||
| Status: | Not Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Funder: | Science Foundation Ireland (SFI), Corpus Christi College (University of Cambridge), Engineering and Physical Sciences Research Council (EPSRC) |
Data sourced from Thomson Reuters' Web of Knowledge
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