Author

Xiaobo Li

Date of Award

2011

Level of Access

Campus-Only Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor

Howard H. Patterson

Second Committee Member

Alice E. Bruce

Third Committee Member

Scott Collins

Abstract

The photophysical and photochemical properties of NaCu(CN)2 and KCu(CN)2 in bulk and doped in alkali halide hosts have studied. In addition, heterometallic interaction between d10-d10 (Cu(CN)2--Au(CN)2- and Cu(CN)2--Ag(CN)2-) and d8-d10 (Ni(CN)42--Cu(CN)2-, Pd(CN)42--Cu(CN)2- and Pt(CN)42--Cu(CN)2-) doped in alkali halide hosts have been investigated. All crystals have been synthesized and analyzed by various characterization and spectroscopy measurements, such as atomic absorption, FT-IR, Raman, UV-Vis reflectance, and luminescence. Experimental results provide the evidence for the formation of [Cu(CN)2-]n nanoclusters, which leads to the interesting emission tunability, thermochromism, and optical memory behavior of Cu(CN)2- doped in alkali halide systems. Emission peaks from d10-d10 and d8-d10 heterometallic interaction have been observed as well. Theoretical calculations have been conducted and the results show excimer and exciplex behavior for these alkali halide doped systems. These luminescence peaks are from metal-to-ligand charge transfer and metal-metal-to-ligand charge transfer transitions.

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