From Coordination Complexes To Conductive Polymers

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From Coordination Complexes to Conductive Polymers

The field of synthetic chemistry provides an unparalleled opportunity to study the relationship between molecular structure and the physical and chemical properties of a system. Toward this end, this dissertation describes efforts to develop new systems containing negatively charged components with an eye toward applying them to energy storage applications. Chapter One begins by explaining the importance of energy storage in harnessing renewable energy sources and how photosynthesis can serve as inspiration for converting solar energy into useful chemical fuels. It also outlines the motivation and core concepts for projects described in later chapters. Chapter Two is presented in two parts. The first describes the synthesis of a series of ruthenium complexes bearing the pentadentate ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2) and the subsequent electrochemical evaluation of [(PY5Me2)Ru(H2O)]2+ as a water oxidation catalyst. The second investigates [(PY5Me2)Co(H2O)]2+ for the same application. While both systems provided initial electrochemical evidence for water oxidation, it was ultimately found that the ruthenium complex served only as a stoichiometric oxidant for water oxidation while the cobalt complex appeared to decompose to a catalytically active side product. Based on lessons learned in Chapter Two, a fresh initiative was undertaken to synthesize new ligand scaffolds that might better support the high-valent metal species necessary to perform water oxidation. Consequently, pentadentate ligands possessing anionic donors were pursued. Chapter Three presents the synthesis and characterization of alkali metal salts of the tetraanionic ligand 2,2′-(pyridine-2,6-diyl)bis(2-methylmalonate) ([PY(CO2)4]4−) via deprotection of the neutral tetrapodal ligand tetraethyl 2,2′-(pyridine-2,6-diyl)bis(2-methylmalonate) (PY(CO2Et)4). The [PY(CO2)4]4− ligand, which features an axial pyridine and four equatorial carboxylate groups, cleanly reacts with a number of divalent first-row transition metals to form the series of complexes K2[(PY(CO2)4)M(H2O)] (M = Mn2+, Fe2+, Co2+, Ni2+, Zn2+). The metal complexes were comprehensively characterized via single-crystal X-ray diffraction, 1H NMR and UV-Vis absorption spectroscopy, and cyclic voltammetry. Additionally, Chapter Three recounts a barrage of synthetic routes that have been attempted in order to generate a new N4C− ligand possessing four equatorial pyridine donors and an axial, anionic carbon donor. While this ligand has not yet been successfully isolated in sufficient amounts, the most promising options moving forward are highlighted. Although the final chapter continues to focus on the synthesis of negatively charged systems, the desired application switches to that of single-ion conducting electrolytes for Li-ion batteries. Hence, Chapter Four reports the synthesis of a series of poly(ethylene glycol) (PEG) based network polymers incorporating fluorinated tetraphenylborate nodes into the polymer backbone. The modular nature of the building units for this polymer allowed for a systematic study of the effect of linker length and composition on the conductivity of Li-ions through the material. Whereas long linkers produced flexible materials that were conductive at elevated temperatures, materials made with short linkers were brittle and exhibited no conductivity. However, when loaded with 68 wt% propylene carbonate, materials containing short linkers outperformed those with long linkers, exhibiting conductivity as high as 2.5 × 10–4 S/cm for the polymer made with ethylene glycol. It was also found that the conductivity could be further increased by exchanging the PEG linker for 1,5-pentanediol, which produced conductivity values of 3.5 × 10–4 S/cm.
Conductive Polymers and Their Composites

This book provides a comprehensive overview on the recent significant advancements of conductive polymers and their composites in terms of conductive mechanism, fabrication strategies, important properties, and various promising applications. The corresponding knowledge was systematically compiled in the logical order and demonstrated as seven chapters. The special structure, influencing factors of the conductivity, the charge carrier transport model, the wettability and classical categories of the conductive polymers are narrated. Both conventional and novel strategies undertaken to fabricate the conductive polymers are introduced, as provided the overall master of the progress. In comparison with the bulk counterpart, nanostructured conductive polymers with different dimensions such as nanospheres, nano-networks, nanotubes and nanowire arrays are produced through distinct methods, thus presenting unique and distinct performance endowed by the nanometer scale. The combination of conductive polymers with other functional materials results in a number of the composites with improved properties by synergistic effect. The superior performance of conductive polymers and their composites greatly facilitates their development toward various important applications in the advanced and sophisticated fields such as biological utilization, energy storage and sensors. Due to their excellent biocompatibility, conductive polymers and their composites stand out to be useful in the biological field including tissue engineering, drug delivery and artificial muscle. To meet the urgent demand of the energy storage, conductive polymers and their composites play an important role in the devices including supercapacitors, solar cells and fuel cells. Finally, development of conductive polymers and their composites in the modern industry is greatly enhanced by their applications in smart sensors such as conductometric sensors, gravimetric sensors, optical sensors, chemical sensors and biosensors. This book has significant value for researchers, graduate students, and engineers carrying out the fundamental research or industrial production of conductive polymers and their composites.
Catalysis by Polymer-Immobilized Metal Complexes

Deals with a new and promising field developed during the last two decades on the boundary between homogeneous and heterogeneous catalysis. This book presents general information on catalysis for a wide range of organic reactions, e.g., hydrogenation and oxidation reactions, and polymerization transformations. Special attention is paid to electro- and photochemical stimulation of catalytic processes in the presence of immobilized metal complexes. Other topics covered are the quantitative data on the comparison of catalyses by mobile and immobilized metal complexes; main factors affecting the activity of these catalytic systems and methods of optimizing their control; and specific problems of catalysis by fixed complexes (e.g., ligand exchange and electron transfer in metal polymer systems, macromolecular effects and polyfunctional catalysis).