Year of Publication

2007

Document Type

Dissertation

College

Arts and Sciences

Department

Chemistry

First Advisor

Dong-Sheng Yang

Abstract

Copper-organonitrogen complexes are studied by threshold photoionization and zero electron kinetic energy photoelectron spectroscopy. These complexes are prepared in pulsed laser vaporization supersonic molecular beams. Adiabatic ionization energies of the neutral species and vibrational frequencies of the neutral and ionic complexes were measured. Metal-ligand bond dissociation energies were obtained from the theoretical calculations or the experiments. More importantly, by combining the spectroscopic measurements, quantum chemical calculations, and spectral simulations, metal-ligand bonding structures are determined for copper complexes of diamines, pyridine, diazines, aminopyridines, polypyridines, and imidazole. The Cu-ethylenediamine, -(1,3-propanediamine), and -(1,4-butenediamine) complexes have been determined to be in a hydrogen-bond stabilized monodentate configuration. However, Cu atom binds to both two nitrogens in the methyl-substituted ethylenediamines. The change of the Cu binding from the monodentate to the bidentate mode arises from the competition between copper coordination and hydrogen bonding. Although pyridine, diazines, and imidazole molecules can function as a s-donor through the nitrogen atom, a p-acceptor or p-donor through six-membered or five-membered aromatic ring, only the s bonding mode is predicted by the theory and identified by the ZEKE spectroscopy. For aminopyridine molecules, s bonding through the sp2 or sp3 hybrid electron lone pair and p bonding through the pyridine ring are possible. Yet, the s bonding through the sp2 electron donation is calculated to be the strongest, and the Cuaminopyridine complexes formed by such bonding mechanism are identified by the experiments. Moreover, monodentate Cu-(4,4'-bipyridine), bidentate Cu-(2,2'-bipyridine) and Cu-(1,10-phenanthroline), and tridentate Cu-(2,2':6',2?-terpyridine) are established to be the most stable structure and are observed by experiments. It is surprising to find that the tridendate planar structure of Cu-(2,2':6',2?-terpyridine) changes to a twisted Cs structure upon ionization.

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