Date of Award

2018

Publication Type

Doctoral Thesis

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

NMR; Porous materials; Solid-state NMR

Supervisor

Schurko, Robert

Rights

info:eu-repo/semantics/openAccess

Abstract

The work described herein demonstrates the utility of solid-state nuclear magnetic resonance (SSNMR) spectroscopy for the characterization of molecular-level structure and dynamics in porous materials, including the determination of the reaction pathways involved in the formation of porous solids made via solid-state synthetic techniques, a study of the motion of dynamic components of metal-organic frameworks (MOFs) that are prototypes for future molecular machines, and the structural characterization of a surface-supported catalyst. In Chapters 2 and 3, accelerated aging and mechanochemical reactions are used to synthesize cadmium-containing zeolitic imidazolate frameworks (ZIFs). These techniques provide a means for clean and efficient syntheses of these materials; however, little is known about the reaction kinetics and mechanisms underlying their production. First, the structure of a new cadmium-imidazolate framework (CdIF) is determined using a combination of powder X-ray diffraction (PXRD) and SSNMR, a methodology known as NMR-assisted crystallography. SSNMR experiments are also used to monitor the formation of ZIFs made using mechanochemical synthesis, providing information on the intermediates and products of the reactions. It is revealed that the initial mechanochemical ball milling provides the activation energy for the formation of ZIFs, but aging reactions within the milling jars drive the reaction to completion. As demonstrated here, milling times as short as five seconds provide enough energy for the initiation of the reactions, allowing for extremely low-energy synthesis of these materials. In Chapter 4, series of metal-organic frameworks (MOFs) with dynamic, interlocked crown ether rings are investigated to determine the factors that influence the motion of the rings. It is demonstrated that the size of the rings and the framework structure affect the motion. 13C variable temperature SSNMR is used to confirm the shuttling motion of rings between recognition sites on an axle that is incorporated into a MOF. Next, a study on a series of simple inorganic molecular rotors is described. It is shown that some of these compounds act as rotors with very low energy barriers that exhibit random rotational dynamics at temperatures below 75 K, while other structurally similar compounds do not display any motions over a wide range of temperatures. It is posited that steric and electronic effects from the coordinating ligands are responsible for the observed dynamics. 2H SSNMR is shown to be essential for classifying and understanding the dynamics of these low-energy molecular rotors Finally, 35Cl SSNMR is used to elucidate the structure of a transition-metal compound bound to the surface of a porous silica material. It is demonstrated that ultra-wideline (UW) 35Cl SSNMR spectra for transition-metal complexes can be rapidly acquired using a combination of high magnetic fields and specialized pulse sequences. These spectra allow for the differentiation of different Cl bonding environments (i.e., bridging, terminal axial, and terminal equatorial). Density functional theory (DFT) calculations and an accompany molecular-orbital analysis allow for an understanding of the origin of the observed 35Cl electric field gradient (EFG) parameters, which influence the 35Cl quadrupolar interactions. The structure of a surface-supported complex is then proposed, demonstrating the applicability of these techniques to the study of very dilute catalytic species.

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