Webber, Amy L., Yates, Jonathan R., Zilka, Miri, Sturniolo, Simone, Uldry, Anne-Christine, Corlett, Emily K., Pickard, Chris J., Pérez-Torralba, Marta, Angeles Garcia, Maria, Santa Maria, Dolores, Claramunt, Rosa M. and Brown, Steven P. (2020) Weak intermolecular CH···N hydrogen bonding : determination of 13CH-15N hydrogen-bond mediated J couplings by solid-state NMR spectroscopy and first-principles calculations. The Journal of Physical Chemistry A, 124 (3). pp. 560-572. doi:10.1021/acs.jpca.9b10726 ISSN 1089-5639.

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Abstract

Weak hydrogen bonds are increasingly hypothesised to play key roles in a wide range of chemistry from catalysis to gelation to polymer structure. Here, 15N/13C spin-echo magic-angle spinning (MAS) solid-state NMR experiments are applied to “view” intermolecular CH···N hydrogen bonding in two selectively labelled organic compounds, 4-[15N] cyano-4’-[13C2] ethynylbiphenyl (1) and [15N3,13C6]-2,4,6-triethynyl-1,3,5-triazine (2). The synthesis of 2-15N3,13C6 is reported here for the first time via a multistep procedure, where the key element is the reaction of [15N3]-2,4,6-trichloro-1,3,5-triazine (5) with [13C2]-[(trimethylsilyl)ethynyl]zinc chloride (8) to afford its immediate precursor [15N3,13C6]-2,4,6-tris[(trimethylsilyl)ethynyl]-1,3,5-triazine (9). Experimentally determined hydrogen-bond mediated 2hJCN couplings (4.7 ± 0.4 Hz (1), 4.1 ± 0.3 Hz (2)) are compared with density functional theory (DFT) gauge-including projector augmented wave (GIPAW) calculations, whereby species independent coupling values 2hKCN (28.1 (1), 26.1 (2) × 1019 kg m–2 s–2 A–2) quantitatively demonstrate the J couplings for these CH···N hydrogen bonds to be of a similar magnitude to those for conventionally observed NH···O hydrogen-bonding interactions in uracil (2hKNO: 28.1 and 36.8 × 1019 kg m–2 s–2 A–2).

Item Type:	Journal Article
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Physics
Library of Congress Subject Headings (LCSH):	Weak interactions (Nuclear physics), Nuclear magnetic resonance spectroscopy, Hydrogen bonding, Chemical bonds, Organic solid state chemistry, Organic compounds -- Synthesis
Journal or Publication Title:	The Journal of Physical Chemistry A
Publisher:	American Chemical Society
ISSN:	1089-5639
Official Date:	23 January 2020
Dates:	Date Event 23 January 2020 Published 27 December 2019 Available 27 December 2019 Accepted
Volume:	124
Number:	3
Page Range:	pp. 560-572
DOI:	10.1021/acs.jpca.9b10726
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Copyright Holders:	Copyright © 2019 American Chemical Society
Date of first compliant deposit:	9 January 2020
RIOXX Funder/Project Grant:	Project/Grant ID RIOXX Funder Name Funder ID EP/J010510/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266 EP/M022501/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266 EP/L015307/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266 EP/C007573/1 [EPSRC] Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266 CTQ2014-56833R [MINECO] Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 316630 CAS-IDP FP7 People: Marie-Curie Actions http://dx.doi.org/10.13039/100011264 UNSPECIFIED [RS] Royal Society http://dx.doi.org/10.13039/501100000288
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