Development of luminescent coinage metal materials for use as small molecule sensors.

摘要

This work describes the development of two types of functional luminescent materials. These materials, which incorporate the coinage metals silver(I) and copper(I), hold considerable promise as components of sensor technologies or in energy-conversion devices. The first materials comprise silver(I)-impregnated films of poly(vinylphenylketone), polystyrene, and the oligomer 1,4-bis(methylstyryl)benzene. These films were developed as chemical sensors of the plant hormone ethylene. The second materials comprise a family of sterically hindered copper(I)-phenanthroline complexes synthesized through a recently reported oxidation-based method. These copper(I) complexes possess desirable spectroscopic properties, and could be employed in energy conversion devices.;Ethylene is a hormone that regulates a number of developmental processes in plants and their commercial products. Accidental exposure to ethylene can result in premature rotting of produce. As such, plants and their products are typically stored and transported in conditions that limit their exposure to ethylene; however, there is a need for a reliable and inexpensive ethylene sensor that could monitor evolution of the gas in storage and transportation spaces. Chapter 2 describes the ethylene-sensing capabilities of silver(I)-impregnated films of poly(vinylphenylketone), polystyrene, and the oligomer 1,4-bis(methylstyryl)benzene. These films demonstrate a proportional and reversible quench in emission upon exposure to ethylene pressures. The breadth of the sensing capabilities of the films, the nature of the observed emission quench, and the morphology of these films are described.;Chapter 3 describes the synthesis and spectroscopic characterization of a family of copper(I)-phenanthroline complexes, including [Cu(2,9-di- tert-buty1-4,7-di-phenyl-1,10-phenanthroline)2][SbF 6] ([Cu(dtbbp)2][SbF6]). The absorption and emission spectra of this complex in dilute solutions of CH2Cl2 show significant similarities to that of a mixture of [Cu(2,9-di- tert-butyl-4,7-di-pheny1-1,10-phenanthroline)(acetone)][SbF 6] and free phenanthroline ligand, which indicates the dissociation of [Cu(dtbbp)2][SbF6] in dilute solutions. In contrast, solid-state spectroscopic characterization of the same complex reveals strong absorption and emission bands, which are characteristic of bis-ligated copper(I)-phenanthroline complexes. Structural characterization of [Cu(dtbbp)2][SbF 6] reveals considerably long Cu-N bond distances, which might account for the facile dissociation of this complex in the presence of weakly binding ligands and in dilute solutions.