Date of Graduation

Fall 2010

Degree

Master of Science in Chemistry

Department

Chemistry

Committee Chair

Nikolay Gerasimchuk

Keywords

Ag(I) cyanoximates, silver photochemistry, cyanoximes, high-energy dosimeters, colorimetric sensors.

Subject Categories

Chemistry

Abstract

Eleven silver(I) complexes with cyanoxime ligands, abbreviated as L, having the general formula NC-C(=NOH)-R where R is an electron-withdrawing group, were synthesized and characterized using the infrared solid-state, ultraviolet-visible spectroscopy and X-ray analysis (powder and single crystal). All eleven synthesized silver(I)L complexes have bright and unusual (for silver(I) compounds) color ranging from yellow, orange, to a deep purple. Crystal structures revealed formation of 2-dimensional coordination polymers with cyanoxime anions acting as bridging ligands using both N and O atoms of the >CNO fragment for binding metal ions. Bond lengths between silver(I) centers and anions in these polymers are significantly shorter than the sum of ionic radii of donor atoms (Oxygen, or Nitrogen) and metal centers, which provide evidence for their significantly covalent character. Due to this fact, silver(I) cyanoximates demonstrate remarkable visible light insensitivity, and also considerable resistance towards short wavelength UV (254 nm) radiation. Detailed photodegradation studies under direct UV-radiation were carried out for all eleven Ag(I) cyanoximates. Prolonged exposure to UV-light results in formation of nano-sized metal silver particles.

Copyright

© Jeffrey Richard Morton

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