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A novel synthetic methodology has been developed for attaching fluorene derivatives, containing different types of electron donating and accepting groups at the 2 and 7 positions, to gold nanoparticles of different sizes by exploiting the affinity of the thiol functional group for gold. The distance between the dye and nanoparticles was varied by introducing two alkyl chains containing different number of carbon atoms at the 9 position on the fluorene ring system. The methodology that was developed gave enough scope for performing Radiative Decay Engineering (RDE) studies, in order to investigate the impact of gold nanoparticles on the singlet oxygen quantum yields of fluorene dyes that already exhibit high singlet oxygen quantum yields as well as high two photon absorption (2PA) cross-sections. The dialkylation of the fluorene derivatives was accomplished by reacting the dye with [alpha], [omega]-dibromoalkanes containing different number of carbon atoms in a biphasic reaction mixture containing toluene and aqueous sodium hydroxide solution in the presence of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The bromine atom on the alkyl chains was converted to thioester by reaction with potassium thioacetate. This was followed by the hydrolysis of the thioester to form the thiol moiety. The compounds synthesized were characterized using 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Functionalization of gold nanoparticles was attempted by bringing into contact a solution of the thiol compound in toluene and an aqueous gold nanoparticles solution. UV-vis absorbance spectroscopy was used to monitor the progress of the attachment. Surface Enhanced Raman Scattering (SERS) spectroscopy was used to probe the enhancement of Raman signal by the metallic nanoparticles.

Indiana University-Purdue University Indianapolis (IUPUI) / Alkyl radicals are powerful intermediates for the generation of carbon-carbon bonds, which play an indispensable role in the synthesis of natural products, pharmaceuticals, and pesticides. Traditionally, there are two main methods for the generation of alkyl radicals. The first is C-H bond functionalization via hydrogen-atom-transfer (HAT). HAT processes have been used as an effective approach for selectively activating C-H bonds via radical pathways. The other strategy to explore the generation of alkyl radicals is C-X bond functionalization via halogen-atom-transfer (XAT). Alkyl halides are one of the largest classes of building blocks in synthesis and they can be obtained from the corresponding alcohols. The most straightforward and effective way to form such alkyl radicals is the direct homolytic cleavage of C-X bonds. In past decades, photoredox catalysis has emerged as a powerful and greener tool for the synthesis of radicals under mild reaction conditions, which has brought tremendous attention. Although remarkable success has been made in this field, some methods still require costly transition metal catalysts or toxic reagents. Herein, we display a series of visible light-induced approaches under transition-metal free conditions or using earth-abundant metals. These novel photo-induced transformations and corresponding mechanistic work will be discussed in the following order: We will first present our work on metal-free visible-light-promoted C(sp3)-H functionalization of aliphatic cyclic ethers using trace O2. This reaction uses a trace amount of aerobic oxygen as the sole green oxidant under blue light at room temperature to achieve the synthesis of sulfone and phosphate derivatives in good to excellent yields using cyclic ethers and vinyl sulfones. Then, we report on a photo-induced C(sp3)-H chalcogenation of amide derivatives and ethers via a ligand-to-metal charge-transfer. This reaction converts secondary and tertiary amides, sulfonamides, and carbamates into the corresponding amido-N,S-acetal derivatives in good yields, using an earth abundant metal catalyst under mild conditions. Finally, we present a photoredox polyfluoroarylation of alkyl halides via halogen atom transfer. This method converts primary, secondary, and tertiary unactivated abundant alkyl halides into the corresponding polyfluoroaryl compounds in good yields and has good functional group compatibility.

Light hydrocarbons activations, functionalization, and reactions have been a subjects of catalysis research for decades but dominated by the rarer and more expensive noble metals. Switching over to using the more earth abundant third row transition metals could be more economical and less toxic but come with their own challenges. Their use as catalysts with light hydrocarbons could be employed better utilize and more efficiently use our hydrocarbon resources that the world still depends on.

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<p>The thermal azide-alkyne cycloaddition using electron deficient alkynes was used to functionalize polysiloxanes at low temperatures and without the need of a metal catalyst. We observed that the temperature at which cycloaddition began can be attributed to the identity of the alkyne's substituents (Chapter 2). We propose that the location of functionalization can be controlled by the specific introduction of electron deficient alkynes on terminal or pendant points on the polysiloxane. Polysiloxanes, each containing two electronically different alkynes, were prepared to show preferential functionalization of the more reactive alkyne without consuming the less reactive alkyne. The alkyne's reactivity can be modified by our choice of substituents. The extension of these results led to polysiloxane difunctionalization where the more reactive alkyne was consumed by a small azide followed by consumption of the less reactive alkyne with a bisazide siloxane. Thermal cycloaddition was used to introduce carbohydrates onto polysiloxanes without complicated protection/deprotection schemes and without catalysts (Chapter 3). The process was successful as propiolate-functionalized siloxane and azide-functionalized gluconamide reacted to produce a trisiloxane-functionalized gluconamide. Trisiloxane-functionalized gluconamide gelled diethyl ether at 3.0% gelator/solvent volume ratio becoming one of the few siloxane-based gelling agents.</p> / Master of Science (MSc)