{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,5]],"date-time":"2026-03-05T20:27:12Z","timestamp":1772742432861,"version":"3.50.1"},"reference-count":61,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2012,3,20]],"date-time":"2012-03-20T00:00:00Z","timestamp":1332201600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2012,4,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Multinuclear (<jats:sup>31<\/jats:sup>P and <jats:sup>79\/81<\/jats:sup>Br), multifield (9.4, 11.75, and 21.1\u2005T) solid\u2010state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single\u2010crystal X\u2010ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh<jats:sub>4<\/jats:sub>, because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non\u2010standard nuclei can correct or improve X\u2010ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, <jats:sup>79\/81<\/jats:sup>Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. <jats:sup>35\/37<\/jats:sup>Cl solid\u2010state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge\u2010including projector\u2010augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, <jats:italic>\u03b4<\/jats:italic><jats:sub>11<\/jats:sub>, on the shortest Br\uf8ffP distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey\u2019s theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such as <jats:sup>79\/81<\/jats:sup>Br, can afford insights into structure and bonding environments in the solid state.<\/jats:p>","DOI":"10.1002\/chem.201103478","type":"journal-article","created":{"date-parts":[[2012,3,20]],"date-time":"2012-03-20T11:43:29Z","timestamp":1332243809000},"page":"5748-5758","source":"Crossref","is-referenced-by-count":23,"title":["A Combined Solid\u2010State NMR and X\u2010ray Crystallography Study of the Bromide Ion Environments in Triphenylphosphonium Bromides"],"prefix":"10.1002","volume":"18","author":[{"given":"Kevin M. 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