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dc.contributor.authorAshbrook, Sharon E.
dc.contributor.authorDawson, Daniel M.
dc.contributor.authorGan, Zhehong
dc.contributor.authorHooper, Joseph Edward
dc.contributor.authorHung, Ivan
dc.contributor.authorMacfarlane, Laurie E.
dc.contributor.authorMcKay, David
dc.contributor.authorMcLeod, Lucy K.
dc.contributor.authorWalton, Richard I.
dc.date.accessioned2021-08-03T23:39:08Z
dc.date.available2021-08-03T23:39:08Z
dc.date.issued2020-08-04
dc.identifier.citationAshbrook , S E , Dawson , D M , Gan , Z , Hooper , J E , Hung , I , Macfarlane , L E , McKay , D , McLeod , L K & Walton , R I 2020 , ' Application of NMR crystallography to highly disordered templated materials : extensive local structural disorder in the gallophosphate GaPO-34A ' , Inorganic Chemistry , vol. Article ASAP . https://doi.org/10.1021/acs.inorgchem.0c01450en
dc.identifier.issn0020-1669
dc.identifier.otherPURE: 269344830
dc.identifier.otherPURE UUID: bdf53a07-3129-4748-84d3-7bbccd0ca230
dc.identifier.otherORCID: /0000-0002-4538-6782/work/78527890
dc.identifier.otherORCID: /0000-0002-8110-4535/work/78527963
dc.identifier.otherORCID: /0000-0003-0362-7848/work/78528195
dc.identifier.otherWOS: 000562989200045
dc.identifier.otherScopus: 85089711164
dc.identifier.urihttp://hdl.handle.net/10023/23710
dc.descriptionSEA, DMD, JEH and DM thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. SEA would like to thank the Royal Society and the Wolfson Foundation for a merit award. The National High Magnetic Field Laboratory is supported by National Science Foundation Cooperative Agreement DMR-1644779 and the State of Florida.en
dc.description.abstractWe present an NMR crystallographic investigation of two as-made forms of the recently characterised gallophosphate GaPO-34A, which has an unusual framework composition with a Ga : P ratio of 7 : 6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of these of five, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond timescale, which can be supported by averaging the 31P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present.
dc.language.isoeng
dc.relation.ispartofInorganic Chemistryen
dc.rightsCopyright © 2020 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.inorgchem.0c01450en
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subject.lccQDen
dc.titleApplication of NMR crystallography to highly disordered templated materials : extensive local structural disorder in the gallophosphate GaPO-34Aen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.0c01450
dc.description.statusPeer revieweden
dc.date.embargoedUntil2021-08-04


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