Conformational properties of monosubstituted cyclohexane guest molecules constrained within zeolitic host materials. A solid-state NMR investigation

Abstract

The conformational properties of monosubstituted cyclohexane guest molecules (C6H11X with X = CH3, OH, Cl, Br and I) included within microporous solid host materials (silicalite-I, H-ZSM-5, NH4-mordenite and zeolite NH4-Y) have been elucidated via high-resolution solid-state 13C NMR spectroscopy. For all of the inclusion compounds investigated, the fraction of monosubstituted cyclohexane molecules in the equatorial conformation is similar to that in solution, suggesting that these host materials do not impose any significant constraints upon the conformational properties of the monosubstituted cyclohexane guest molecules. For the monohalogenocyclohexane guest molecules (C6H11X with X = Cl, Br and I), this result is in marked contrast to the situation for the same guest molecules in the thiourea host structure, for which the conformational properties of the guest molecules are substantially different from those of the same molecules in solution. For cyclohexanol (C6H11OH) in H-ZSM-5, some amount of dicyclohexyl ether (C6H11OC6H11) is observed, and is analogous to the proposed production of dimethyl ether in the first stage of methanol-to-gasoline conversion on this zeolite. The comparatively low temperature (ambient temperature) at which this conversion from cyclohexanol to dicyclohexyl ether occurs is noteworthy. In addition to our high-resolution solid-state 13C NMR studies of these materials, 1H MAS and 27AI MAS NMR spectra have also been recorded, and are discussed.