Clathrate Structure Determination by Combining Crystal Structure Prediction with Computational and Experimental 129Xe NMR Spectroscopy. Issue 22 (14th February 2017)

• Record Type: Journal Article
• Authors: Selent, Marcin; Nyman, Jonas; Roukala, Juho; Ilczyszyn, Marek; Oilunkaniemi, Raija; Bygrave, Peter J.; Laitinen, Risto; Jokisaari, Jukka; Day, Graeme M.; Lantto, Perttu
• Is Part Of: Chemistry. Volume 23:Issue 22(2017)
• Page Start: 5258
• Page End: 5269
• Publication Date: 2017-02-14
• Subjects: computational chemistry -- crystal structure prediction -- density functional theory -- first principles modelling -- Xe NMR spectroscopy; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201604797
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: An approach is presented for the structure determination of clathrates using NMR spectroscopy of enclathrated xenon to select from a set of predicted crystal structures. Crystal structure prediction methods have been used to generate an ensemble of putative structures of o ‐ and m ‐fluorophenol, whose previously unknown clathrate structures have been studied by 129 Xe NMR spectroscopy. The high sensitivity of the 129 Xe chemical shift tensor to the chemical environment and shape of the crystalline cavity makes it ideal as a probe for porous materials. The experimental powder NMR spectra can be used to directly confirm or reject hypothetical crystal structures generated by computational prediction, whose chemical shift tensors have been simulated using density functional theory. For each fluorophenol isomer one predicted crystal structure was found, whose measured and computed chemical shift tensors agree within experimental and computational error margins and these are thus proposed as the true fluorophenol xenon clathrate structures. Abstract : 129 Xe NMR/CSP crystallography : A new method to determine the structure of porous solids provides the likely ortho ‐ and meta ‐fluorophenol xenon clathrate structures. They are selected from an ensemble of hypothetical host frameworks generated by crystal structure prediction (CSP) by comparing the 129 Xe powder NMR spectra with detailed NMR shielding tensor first principles calculations.