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Title:Deuterium Solid State NMR Studies of Pyridine Intercalation Compounds
Author(s):McDaniel, Paula LaRayne
Doctoral Committee Chair(s):Jonas, Jiri
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Physical
Abstract:A quadrupole echo deuterium NMR lineshape study on polycrystalline samples of perdeuterated pyridine and selectively deuterated d$\sb2$-pyridine intercalated into 2H-TaS$\sb2$ was performed between 280K and 393K. The powder pattern lineshapes above 333K show signs of motional narrowing. A short spin-lattice relaxation (T$\sb1$) component, attributed to the motionally narrowed lineshape component, showed a sharp decrease corresponding with their appearance in the lineshape. The narrowing motion was found to be rapid rotational diffusion of the pyridine molecule about an axis perpendicular to the C$\sb2$ symmetry axis and parallel to the molecular plane. The orientation of the pyridine in the van der Waals gap is also proposed.
Quadrupole echo deuterium NMR lineshapes of perdeuterated pyridine intercalated into CdPS$\sb3$ were obtained between 260K and 360K. At temperatures greater than 280K, motional narrowing of the pyridine was observed due to a large amplitude reorientational motion in addition to low amplitude librations. The effect of the CdPS$\sb3$ host material on the intercalated molecule is compared to that of 2H-TaS$\sb2$.
The effect of host material compression on the dynamics of the intercalated molecule was investigated using newly developed high pressure $\sp2$H solid state NMR techniques. The apparatus is detailed and the lineshapes collected at 270K, 300K, 330K and 360K on (C$\sb5\sp2$H$\sb5$N)$\sb{.41}$CdPS$\sb3$ are examined. The effect of pressure on the transition between motionally narrowed and rigid pyridine is analyzed using the Clausius-Clapeyron equation.
In an effort to understand the guest/host interaction, a study of pyridine intercalated into H$\sb{.5}$MoO$\sb3$ was undertaken using variable temperature $\sp2$H solid state NMR techniques. The van der Waals gap in the hydrogen molybdenum bronze has a zig-zag configuration which strongly hinders rapid rotational diffusion of the intercalated pyridine.
Issue Date:1988
Description:107 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988.
Other Identifier(s):(UMI)AAI8908773
Date Available in IDEALS:2014-12-15
Date Deposited:1988

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