title: Solid state NMR method for the determination of 3D zeolite framework/sorbate structures: 1H/29Si CP MAS NMR study of the high-loaded form of p-xylene in ZSM-5 and determination of the unknown structure of the low-loaded form.
abstract: A general protocol is described for structure determinations of organic sorbate-zeolite complexes based on the selective, through-space, distance-dependent transfer of magnetization from protons in selectively deuterated organics to framework silicon nuclei. The method was developed using the known structure of the high-loaded ZSM-5/p-xylene complex containing p-xylene-d(6) or p-xylene-d(4). It was then applied to determine the unknown structure of the low-loaded ZSM-5/p-xylene complex using NMR alone. For the high-loaded complex improved data were obtained below 273 K, where slow motions and exchange processes of the p-xylene are eliminated. The general approach was validated by the exact agreement of the experimental (1)H-(29)Si CPMAS spectra obtained at a specific contact time and the complete 24-line spectra simulated using 1/T(CP) vs M(2) correlations from only the six clearly resolved resonances. For the low-loaded complex the (29)Si resonances were assigned at 267 K, and variable contact time CP experiments were carried out between 243 and 173 K using the same specifically deuterated p-xylenes. All possible locations and orientations of the p-xylene guests were sampled, and those solutions that gave acceptable linear 1/T(CP) vs M(2) correlations were selected. The optimum p-xylene location in this temperature range was determined to be in the channel intersection with the long molecular axis parallel to [0,1,0] (ring center fractional coordinates {-0.009, 0.250, 0.541}) with the ring plane oriented at an angle of 30 +/- 3 degrees about the crystallographic b axis. A subsequent single-crystal X-ray study confirmed this predicted structure.
authors.affiliation: Department of Chemistry, University of British Columbia, Vancouver, Canada. fyfe@chem.ubc.ca
authors.forename: Colin A
authors.initials: CA
authors.lastname: Fyfe
authors.forename: Anix C
authors.initials: AC
authors.lastname: Diaz
authors.forename: Hiltrud
authors.initials: H
authors.lastname: Grondey
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Lewis
authors.forename: Hans
authors.initials: H
authors.lastname: Förster
mesh_terms: D003903:Deuterium; D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D011522:Protons; D012825:Silicon; D013011:Sorbic Acid / Q000737:chemistry*; D014992:Xylenes / Q000737:chemistry*; D017641:Zeolites / Q000737:chemistry*
chemical_list: D007554:Isotopes; D011522:Protons; D014992:Xylenes; D017641:Zeolites; D003903:Deuterium; D013011:Sorbic Acid; D012825:Silicon