Self-assembly is an efficient method for generating large numbers of structurally diverse catalysts for screening. In this work, the method of self-assembly was explored in the construction of bifunctional catalysts, from a chiral aminophosphine, 2-formylphenylboronic acid, and a (thio)urea-containing diol. These catalysts were evaluated by their effect on the asymmetric aza-Morita-Baylis-Hillman reaction. In the second half of this thesis, the hydrogen bonding abilities of different dithiosquaramides were analyzed. As thioureas have been shown to be stronger hydrogen bond donors than ureas, it was hypothesized that dithiosquaramides may also follow a similar trend. Affinities of corresponding squaramides and dithiosquaramides to chloride, sulfate, and tosylate were compared, as well as their abilities to catalyze the Freidel-Crafts alkylation between indole and trans-β-nitrostyrene.

Self-assembly of nanorods (NRs) enhanced by functionalization with liquid crystals (LC) ligands has been demonstrated. First, CTAB (cetyltrimethylammonium bromide) coated gold NRs were prepared in water through a modified one-step seed growth process. The hydrophilic GNRs were then converted into hydrophobic NRs employing a surface modification process using liquid crystalline organosilanes. The functionalized GNRs were characterized by TEM (transmission electron microscopy) and SAXS (small angle X-ray scattering) to investigate the packing mode of the GNRs. The results propose models of the assembly of the GNRs depending on nature and connectivity of the attached liquid crystal molecules. Furthermore, a macroscopic orientation of the GNRs doped in LC was achieved via an alignment technique of the liquid crystal host. SAXS analysis of the doped DLC indicated modification of lattice parameters due to the insertion of the DLC-GNRs, which resulted in an enhancement of the charge carrier mobility.

This thesis examines the use of anionic nitrogen chelate ligands in coordination-driven self-assembly and small molecule activation. The two classes of anionic nitrogen chelate ligands that were explored are β-diiminate and 4,5-diazafluorenide derivatives. Chapter 2 deals with Pd β-diiminate chemistry. Chloro-bridged dimers served as versatile starting materials, and their reactivity toward pyridine and arylboronic acids was explored. An unusual transmetallation reaction with arylboronic acids triggered the self-assembly of tetrapallada-macrocycles. The formation of the self-assembled tetrapallada-macrocycles is through the generation of new Pd-C bonds. Chapter 3 deals with 4,5-diazafluorenide as an actor ligand in CO2 activation. A reversible formal insertion of CO2 into a remote ligand C-H bond was discovered. A variety of spectator metal centres were used to tune the reactivity of the actor ligand toward CO2. The spectator metal centre could even be replaced entirely with an organic group allowing for the first metal-free reversible tandem CO2 and C-H activation. Chapter 4 deals with the reactivity of dinuclear Rh 4,5-diazafluorenide-9-carboxylate complexes with dihydrogen in an attempt to reduce the trapped CO2 moiety. A series of stepwise stoichiometric reactions with H2, NMR experiments at low temperatures with added PPh3 or CO2, along with 13C-labelling experiments were conducted in an attempt to identify the products of this reaction and gain some mechanistic insight. Chapter 5 deals with using ambidentate 4,5-diazafluorene derivatives to synthesize linkage isomers, heterobimetallic complexes, and self-assembled macrocycles. The synthesis a new ligand family, 3,6-substituted 4,5-diazafluorene ligands is presented, along with coordination chemistry towards a {RuCp*}+ fragment. Finally in Chapter 6 the coordination chemistry of 3,6-diaryl substituted 4,5-diazafluorene derivatives was explored with the goal of generating low-coordinate species for the activation of small molecules, especially N2. The synthesis of the first trialkylborohydride complex of vanadium is presented.

Polyferrocenylsilane (PFS) diblock copolymers self-assemble in selective solvents to form one-dimensional micelles for a broad range of polymer compositions and experimental conditions, driven by the crystallization of the PFS block that forms the micelle core. The most striking feature of these micelles is that they remain active for further growth. They can be extended in length when additional polymer, dissolved in a good solvent, is added to a solution of the pre-existing micelles. This thesis describes several studies investigating the factors that affect the growth and fragmentation of PFS diblock copolymer micelles in solution, with a particular emphasis on polyisoprene-PFS (PI-PFS) diblock copolymers. The goal of my research was trying to provide deeper understanding of this crystallization-driven self-assembly (CDSA) process. In an attempt to understand the growth kinetics of the PI-PFS cylindrical micelles, I added tiny amount of short micelle seeds into supersaturated solution of the same polymer, and followed the micelle growth by light scattering. The data analysis showed that the increase of micelle length could be described by an expression with two exponential decay terms. In another attempt to examine the factors that may affect the growth behavior of the PI-PFS micelles, I found that PI-PFS long micelles underwent fragmentation when they were subjected to external stimuli, e.g. addition of polar solvent, or heating. During the course of studying the effect of heating on the micelles, I developed a new approach to generate cylindrical micelles with controllable and uniform length, a one-dimensional analogue of self-seeding of crystalline polymers. I carried out a systematic study to investigate the self-seeding behavior of PFS block copolymers.

Polyferrocenylsilane (PFS) diblock copolymers self-assemble in selective solvents to form one-dimensional micelles for a broad range of polymer compositions and experimental conditions, driven by the crystallization of the PFS block that forms the micelle core. The most striking feature of these micelles is that they remain active for further growth. They can be extended in length when additional polymer, dissolved in a good solvent, is added to a solution of the pre-existing micelles. This thesis describes several studies investigating the factors that affect the growth and fragmentation of PFS diblock copolymer micelles in solution, with a particular emphasis on polyisoprene-PFS (PI-PFS) diblock copolymers. The goal of my research was trying to provide deeper understanding of this crystallization-driven self-assembly (CDSA) process. In an attempt to understand the growth kinetics of the PI-PFS cylindrical micelles, I added tiny amount of short micelle seeds into supersaturated solution of the same polymer, and followed the micelle growth by light scattering. The data analysis showed that the increase of micelle length could be described by an expression with two exponential decay terms. In another attempt to examine the factors that may affect the growth behavior of the PI-PFS micelles, I found that PI-PFS long micelles underwent fragmentation when they were subjected to external stimuli, e.g. addition of polar solvent, or heating. During the course of studying the effect of heating on the micelles, I developed a new approach to generate cylindrical micelles with controllable and uniform length, a one-dimensional analogue of self-seeding of crystalline polymers. I carried out a systematic study to investigate the self-seeding behavior of PFS block copolymers.

The research work presented in this thesis investigates the mechanistic details of conventional as well as electrochemically directed self-assembly of alkylthiosulfates and explores the use of conjugated semiconducting polymers for organic electronic applications. Here, the significance of the use of conjugated polymers is twofold; first, to explore their applications in nanoelectronics and second, the possibility of using them as a top contact on the self-assembled monolayers (SAMs) for molecular electronic applications. Throughout this work, deposition of the organic materials was performed on prefabricated device structures that required no further lithographic or metal deposition steps after modification of the electrodes with the organic molecules. Self-assembly of alkylthiosulfates on gold are reported to form monolayers identical to those formed from the corresponding alkanethiols. However, these self-assembly processes follow more complex mechanisms of monolayer formation than originally recognized. Studies on the mechanism of alkylthiosulfate chemisorption on gold shows that the self-assembly process is influenced by electrolyte and solvent. Plausible mechanisms have been proposed for the role of trace water in the solvent on conventional as well as electrochemically assisted self-assembly of alkylthiosulfates on gold. Electroanalytical and spectroscopic techniques have been used to explore the mechanistic details of electrochemically directed self-assembly of alkylthiosulfates on gold. It has been found that the self-assembly process is dynamic under electrochemical conditions and the heterogeneous electron transfer process between the organosulfur compound and gold is mediated through gold surface oxide and accompanied by corrosion. Conducting polymers are serious candidates for organic electronic applications since their properties can be controlled by the manipulation of molecular architecture. Unique electronic properties of conjugated polypyrrole hybrid materials (PPy0DBS-Li+) with immobile dopant anions and mobile cations have been observed and explained on the basis of movement of the cations in an applied electric field. Based on this principle, functioning polymer resistive memory devices have been demonstrated which can be scalable to lower dimensions for nanoelectronics applications. Finally, proof of concept for using a conducting polymer as a top contact in molecular electronic devices created using electrochemically directed self-assembly is demonstrated.

This thesis explores fundamental design strategies in the field of synthetic ion channel research from two different perspectives. In the first part the synthesis of complex, shape persistent and thermodynamically stable structures based on metal-ligand self-assembly is explored. The second part examines transport systems with dynamic transport behavior in response to chemical inputs which more closely mimic the dissipative assembly of Natural ion channels. In part one, two model systems, the ethylenediamine palladium(II) - 4,4’-bipyridine squares of Fujita and the trimeric bis(terpyridine) - iron(II) hexagonal macrocycles of Newkome, were targeted for structural modification towards becoming transport competent systems via improving the membrane partitioning characteristics of the final coordination compounds by increasing their lipophilicity. Modifications of the Fujita system involved the generation of two lipophilic 4,4’-bipyridines with addition of lipophilic groups of 13 and 17 carbon long alkyl chains respectively at the 3 and 3’ positions. After pursuing multiple unsuccessful synthetic routes the successful syntheses afforded the final lipophilic 4,4’-bipyridines in overall yields of 19 to 21% over two synthetic steps. Mixtures of the newly generated lipophilic 4,4’-bipyridines with a known lipophilic ethylenediamine palladium(II) “corner” exhibited evidence of self-assembly from NMR spectroscopy experiments however attempts at further characterization by ESI-MS and X-ray crystallography were unproductive. The putative self-assembled structures were inactive in HPTS vesicle assays but showed erratic conductance activity in bilayer clamp experiments. However, the magnitude of the conductance observed was not indicative of the passage of ions through the internal pore of the square complex. Modifications to the Newkome hexagons were aimed at generating overall neutral assemblies with external lipophilic groups. These modifications involved imparting a net -2 charge to the ligand via modifications to the terminal tridentate ligands so that upon coordination to octahedral metal centers in the +2 oxidation state the overall hexagonal complex would be neutrally charged. Two bis-polydentate ligands were generated; a dissymmetric molecule comprising one terpyridine and one dipicolinate tridentate ligand (TERPY-DPA) and a symmetrical molecule comprising two 2,2’-bipyridine-6-carboxylate tridentate ligands (BIPYA-BIPYA). The successful syntheses provided the desired trimethylsilylethyl ester protected compounds in yields of 9.2 and 7.5 % over 6 and 8 total synthetic steps for TERPY-DPA and BIPYA-BIPYA respectively. A new approach to metal-ligand complex formation by concomitant fluoride deprotection and assembly was demonstrated with a monomeric complex. Polymetallic complexes formed with a variety of transition metals based on colorimetric changes but the products were very intractable and resisted full structural or transport characterization. Part two develops a system potentially capable of exhibiting dissipative assembly of active transporters. A library of six thioester containing compounds structurally related to known active oligoester compounds was synthesized. The successful syntheses provided the desired compounds in overall yields of 1.0 to 17.7% over 11 to 13 total synthetic steps. The intramolecular cyclization - truncation and thioester exchange reactions central to the dissipative assembly strategy were explored using a model compound. The full length compounds showed transport activity via the HPTS vesicle assay that was significantly below that of the lead compound. Bilayer clamp experiments however, revealed significant transport activity for both the full length as well as the truncated thiol molecules. In the case of the latter the transport events had exceedingly high conductivity for such a small molecule. This unexpected activity for both the full length and truncated compounds, although different, prevented a full implementation of dissipative assembly of transport. / Graduate / 0490 / 0485 / 0494

Chiral structure formation is ubiquitous in surface self-assembly. Molecules that do not undergo chiral recognition in solution or fluid phases can do so when their configurational freedom is restricted in the two-dimensional field of a substrate. The process holds promise in the manufacture of functional materials for chiral catalysis, sensing or nonlinear optics. In this thesis, we investigate the influence of surface attraction and geometry on adsorption-induced chiral separation in several model molecules, as well as the relationships between molecular features, specifically molecular geometry and charge distribution, and chiral recognition at surface self-assembly. Simple model molecules embody the fundamental interactions involved in supramolecular structure formation in experimental systems, and allow the in-depth investigation of key parameters. Chiral pattern formation at the surface self-assembly is a complex problem, even in cases where very small organic molecules are considered. Even though the adsorption behaviour of small organic molecules on gold surfaces has been investigated extensively so far experimentally and theoretically, much of their chiral behaviour is yet to be understood at a molecular level. Theoretical investigations of chiral self-assembly of sulfur containing amino acids onto achiral and chiral gold surfaces is also presented in this thesis. By understanding chiral self-assembly on solid surfaces, one may control and direct it towards creating materials with desired functionality. / Graduate / 0494 / tp.popa@gmail.com

Synthesis of nanocrystals is one of the most rapidly advancing areas of nanoscience, and today nanocrystals can be produced with impressive control over their composition, size, shape, polydispersity, and surface chemistry. As such, they are ideal building blocks for fabricating hierarchical architectures with tailorable functionality on every level of the hierarchy. Here an evaporation-driven, template-assisted nanocrystal assembly (ETNA) technique is developed, providing a novel and general approach to fabricating freestanding, 3D, functional architectures using diverse combinations of colloidal nanocrystal species and porous templates of arbitrary geometry. Colloidal PbS (photoluminescent) and CoFe2O4 (superparamagnetic) nanocrystals are template-assembled to fabricate freestanding nanorods and inverse opals, which retain the size-dependent properties of their constituent building blocks while replicating the geometry and preserving the functionality of the templates. Further multifunctionality is demonstrated through mixed-nanocrystal architectures which exhibit the aggregate functionality of their building blocks.

Synthesis of nanocrystals is one of the most rapidly advancing areas of nanoscience, and today nanocrystals can be produced with impressive control over their composition, size, shape, polydispersity, and surface chemistry. As such, they are ideal building blocks for fabricating hierarchical architectures with tailorable functionality on every level of the hierarchy. Here an evaporation-driven, template-assisted nanocrystal assembly (ETNA) technique is developed, providing a novel and general approach to fabricating freestanding, 3D, functional architectures using diverse combinations of colloidal nanocrystal species and porous templates of arbitrary geometry. Colloidal PbS (photoluminescent) and CoFe2O4 (superparamagnetic) nanocrystals are template-assembled to fabricate freestanding nanorods and inverse opals, which retain the size-dependent properties of their constituent building blocks while replicating the geometry and preserving the functionality of the templates. Further multifunctionality is demonstrated through mixed-nanocrystal architectures which exhibit the aggregate functionality of their building blocks.