Date of Award

2013

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Robert W. Schurko

Keywords

Pure sciences, Cisplatin, Nanoparticles, Nuclear magnetic resonance, Platinum, Powder X-ray diffraction, Quantum chemical calculations

Rights

CC BY-NC-ND 4.0

Abstract

This thesis is largely devoted to solid-state NMR (SSNMR) studies of insensitive nuclei, which are challenging to study via conventional NMR experiments due to their low natural abundances, low gyromagnetic ratios, and/or anisotropically broadened powder patterns. SSNMR experiments on insensitive nuclei such as 195 Pt, 89 Y, 65 Cu, 35 Cl, and 14 N hold much promise for elucidation of structure and bonding within inorganic and organometallic systems. Herein, I describe the use of novel NMR pulse sequences and acquisition methodologies, in combination with X-ray diffraction (XRD) techniques and quantum chemical calcuations of NMR interaction tensors, for this purpose. This thesis begins with a brief introduction to NMR, followed by a proof-of-concept multinuclear ( 195 Pt, 14 N, 35 Cl) study on cisplatin and several related square-planar Pt(II) species. This work is extended to the structural determination of Magnus' Pink Salt, in conjunction with refinements of powder XRD data and ab initio calculations. Two further applications of 195 Pt solid-state NMR follow: determination of Pt oxidation state and coordination with hexadentate ligands, and investigation of Pt vapochromism in the Pt(bpy)CN 2 system. NMR experiments involving insensitive 89 Y nuclei, in conjunction with 19 F NMR and powder XRD data, are applied for the structural elucidation of (H 3 O)Y 3 F 10*x H 2 O nanoparticles. Lastly, the use of 65 Cu and 31 P SSNMR for investigation of a series of bis(triphenylphosphine) copper(I) complexes is described. A wide variety of materials may be characterized using information derived from SSNMR experiments on insensitive nuclei, in concert with a combination of complementary techniques.

Comments

6 month

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