Orientation and Motion of Tetrahydrofuran in Graphite-Intercalation Compounds - Proton Nmr-Studies of Cs(Thf)(1.3)C-24 and K(Thf)(2.5)C-24

The orientation and motion of tetrahydrofuran (THF) in the ternary graphite intercalation compounds Cs-(THF)(1.3)C-24 and K(THF)(2.5)C-24 have been studied by proton NMR. Simulations of the NMR spectra indicate that the THF molecules in CS(THF)(1.3)C-24 have their mean planes oriented parallel to the layers of the host lattice, while the THF molecules in K(THF)(2.5)C-24 have their mean planes oriented at an angle between 50 degrees and 75 degrees from the graphite layers. The proton NMR spectra of both compounds show evidence that the THF molecules rotate about the normal to the graphite layers and confirm X-ray diffraction studies showing a degree of orientational disorder in the samples, corresponding to a mosaic spread in the graphite layer orientation. The conformation of the intercalated THF was studied by simulating the experimental NMR spectra using models for the conformational motion of THF. Simulations indicate that the conformation of intercalated THF is different than gas or liquid phase THF, which has been found to have a ring puckering amplitude of 0.38-0.44 Angstrom and to undergo nearly free pseudorotation through a series of conformations. Best agreement between simulated and experimental NMR spectra of Cs(THF)(1.3)C-24 was Obtained with THF interconverting between two conformations of C-s symmetry and a puckering amplitude of 0.30 Angstrom. Free or slightly hindered pseudorotation of THF (observed in liquid or gaseous THF) in this compound produces simulated spectra that differ significantly from the experimental spectra. Simulated proton NMR spectra of K(THF)(2.5)C-24 using conformations of C-s symmetry or free or slightly hindered pseudorotation of THF do not fit the experimental spectra sufficiently well to allow distinction between the conformational motions or to exclude other possible motions.