Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state.
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...N hydrogen bonds in two 6-aminofulvene-1-aldimine derivatives and the ribbon structure formed by a deoxyguanosine...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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2008
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| _version_ | 1797106158037630976 |
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| author | Joyce, SA Yates, JR Pickard, C Brown, S |
| author_facet | Joyce, SA Yates, JR Pickard, C Brown, S |
| author_sort | Joyce, SA |
| collection | OXFORD |
| description | 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...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...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...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. |
| first_indexed | 2024-03-07T06:57:45Z |
| format | Journal article |
| id | oxford-uuid:feb6e94a-20ed-47ab-a57e-8472d483dc3a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:57:45Z |
| publishDate | 2008 |
| record_format | dspace |
| spelling | oxford-uuid:feb6e94a-20ed-47ab-a57e-8472d483dc3a2022-03-27T13:38:43ZDensity functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:feb6e94a-20ed-47ab-a57e-8472d483dc3aEnglishSymplectic Elements at Oxford2008Joyce, SAYates, JRPickard, CBrown, SA 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...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...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...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. |
| spellingShingle | Joyce, SA Yates, JR Pickard, C Brown, S Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title | Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title_full | Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title_fullStr | Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title_full_unstemmed | Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title_short | Density functional theory calculations of hydrogen-bond-mediated NMR J coupling in the solid state. |
| title_sort | density functional theory calculations of hydrogen bond mediated nmr j coupling in the solid state |
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