This thesis is dedicated to developing novel charged Pt(II) complexes and exploring their applications in electroluminescence, bio-imaging and the preparation of soft salts. At the beginning, a brief introduction about the development of ionic transition metal complexes and an overview of their applications in electroluminescence, bio-imaging and soft salts are presented. In chapter 2, a series of anionic Pt(II) complexes were successfully synthesized and fully characterized for their application in electroluminescence with relatively small current density. All the complexes show highly intense emission from blue to red in the solid state but is almost non-emissive in solution. The obtained single crystal data show that the anionic Pt(II) complexes exhibit very large Pt-Pt separation of over 10 Å in the crystal packings due to the bulky counterion [N(n-C4H9)4]+. The strong interactions between adjacent [Pt(C^N)(CN)2]- is thus absent in the solid state and this is considered as the main reason for the different properties in solution and solid state of these anionic complexes. This kind of Pt(II) anionic complexes has also found application in electroluminescence with relatively small current density. A series of novel water-soluble cationic Pt(II) complexes have also been designed and synthesized in chapter 3. Their photophysical properties in both water solution and solid state were investigated. Some of the cationic Pt(II) complexes have been selected to be applied in cell imaging in both live human hepatoma cells (BEL-7402) and mouse embryonic fibroblast (MEF) cells. The results show that these complexes have a much higher cellular uptake in BEL-7402 cells (tumor cells) than in MEF cells (normal cells), indicating these complexes are promising probes for tumor cell imaging. All of the cationic Pt(II) complexes show very low cytotoxicity at low concentration and the cell viability is still assessed to be high even when the concentration increases to 10 μM. The localization of the complexes turned out to be in the cytoplasm and accumulate near the cell nucleus. Attempts have been made to obtain efficient deep-red or NIR Pt(II) complexes by taking advantages of the Pt-Pt interactions in chapter 4. Two Pt(II) soft salts, SS1 and SS2 with bright emission at 674 and 718 nm, have been successfully prepared and characterized. The crystal packing shows a short separation between the two Pt atoms of 3.476 Å and the average distance of two planes of the cyclometalated ligands is 3.360 Å, indicating the existence of strong intramolecular Pt-Pt and π-π interactions. It is the first examples of Pt(II) soft salts bearing strong Pt-Pt interactions and π-π stacking and this has opened a versatile and facile avenue to prepare efficient NIR Pt(II) emitters by taking advantages of the Pt-Pt interactions. SS2 shows different emission in PEG with different concentration and excitation wavelength, indicating their potential application in optical data storage. The electrochromic properties of SS2 have also been investigated considering that the soft salt consists of ions with opposite charges, which suggests the soft salt could be promising candidate for electrochromic and optoelectronic material. The Pt(II) soft salt has also been used as NIR in-vivo imaging probe. Chapters presents the concluding remarks and points out some further work that could be done in the future. The experimental details are displayed in Chapter 6.

This thesis involves reactions of cyclam with Mn(III), Ni(II) and Fe(II). The chemistry of each metal with cyclam will be presented in sections discussing each metal. The initial intent of this thesis was to examine and compare the structures and electronic spectra of a series of trans monomeric first row transition metal cyclam compounds. Both Mn(III) and Ni(II) form such trans monomeric complexes with cyclam and their structural and electronic characteristics are, indeed, examined in this thesis. However, in the course of our study, we found that Fe(II) and cyclam in acetonitrile in the presence of oxygen form a di-macrocycle shown here: [See PDF]

1. The reactions of monochlormethyl ether with the magnesium cadmium and zinc derivatives of normal propyl and isopropyl halides were investigated. 2. In both the normal propyl and iso-propyl aeries, the yields of the expected condensation products RCH₂OCH₃ appeared in the order RMgX>R₂Zn>R₂Cd. 3. The primary organometallic compounds reacted with monochlormethyl ether in higher yields than did the corresponding secondary compounds. 4. A new method was developed for preparing a zinc-copper couple by heating a mixture of zinc dust and powdered cupric citrate under an atmosphere of nitrogen. 5. This method gave a couple superior in laboratory use to the zinc-copper couples how generally employed. / Master of Science

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This report discusses research which was conducted in two areas: the synthesis of potential agrochemicals and the study of vinamidinium and azavinamidinium salt chemistry. Four classes of compounds were synthesized and characterized in the study of new potential agrochemicals. These compounds include diacylhydrazines, semicarbazides, 2,5-disubstituted-1,3,4-oxadiazoles and bis-2,5-disubstituted-1,3,4-oxadiazoles. The reaction of [3-(dimethylamino)-2-azaprop-2-en-1-ylidene] dimethylammonium chloride (Gold's reagent) with organometallic/borane reagents was examined in efforts to find convenient syntheses for N,N-dimethylamino substituted alkyl and aryl compounds. Additionally, the reaction of 1,5-diazapentadienium chloride (Nair's reagent) with nitrile activated alkanes was examined to find a convenient synthesis of 3-substituted pyridines. Subsequent intramolecular ring closure of the dienaminonitriles was unsuccessful. Finally, this report reveals the experimental procedures and conditions used for the synthesis of these products and offers explanations of the data as well as recommendations for future research.