Electronic Thesis and Dissertation Repository

Degree

Master of Science

Program

Chemistry

Supervisor

Dr. John F. Corrigan

Abstract

Previous work using monodentate ferrocenyl-chalcogen reagents for nanocluster surface functionalization has indicated an effective way to involve ferrocene moieties onto the surface of these frameworks. However, the abilities of the large polynuclear nanocluster with ferrocene rich surface to form crystalline materials suitable for single crystal X-ray analysis proved to be limited. New bidentate ferrocenyl-chalcogen reagents have been synthesized and characterized in order to probe their ability in this case.

The preparation of new bidentate ferrocenyl chalcogen reagents 1,1’-fc(C{O}OCH2CH2SH)2 (fc = ferrocenyl) and 1,1’-fc(C{O}NHCH2CH2SH)2 are presented. Furthermore, the preparation of silylated reagent fc(C{O}OCH2CH2SSiMe3)2 and silver thiolate polymer [fc(C{O}OCH2CH2SAg)2] are discussed. The formation of cluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] using Ph2PCH2CH2CH2PPh2 (dppp) solubilized [fc(C{O}OCH2CH2SAg)2] and the sulfide reagent S(SiMe3)2 as precursors is also described. A single crystal X-ray analysis of [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] enables a complete description of the molecule, including the arrangement of the ferrocenyl units on the surface.

Cyclic voltammetry and UV-Vis absorption spectroscopy experiments were conducted on the synthesized ligands, complex and clusters, and the results of these experiments are presented.


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