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Conjugated polymers are gaining a lot of interest due to their inherent functional properties and applications in plastic electronics. Their characteristic charge transporting and conducting properties produces features including coloration, photoluminescence, electroluminescence, photoconductivity, and electrochromism. In order to develop new functional polymers, researchers need the background information on the synthesis of the different polymer systems. Conjugated Polymers focuses on the practical preparation of conjugated polymers with each chapter discussing a particular type of conjugated polymer including a general explanation of the polymer, experimental details for synthesis and characterization. Edited by world leading experts in the field of conjugated polymer synthesis, the book serves as a convenient guide for advanced undergraduate level and above.
Edited and authored by top international experts, this first book on conjugated polymers with a focus on synthesis provides a detailed overview of all modern synthetic methods for these highly interesting compounds. As such, it describes every important compound class, including polysilanes, organoboron compounds, and ferrocene-containing conjugated polymers. An indispensable source for every synthetic polymer chemist.
Many significant fundamental concepts and practical applications have developed since the publication of the best-selling second edition of the Handbook of Conducting Polymers. Now divided into two books, the third edition continues to retain the excellent expertise of the editors and world-renowned contributors while providing superior coverage of
Since their discovery in 1977, the evolution of conducting polymers has revolutionized modern science and technology. These polymers enjoy a special status in the area of materials science yet they are not as popular among young readers or common people when compared to other materials like metals, paper, plastics, rubber, textiles, ceramics and composites like concrete. Most importantly, much of the available literature in the form of papers, specific review articles and books is targeted either at advanced readers (scientists/technologists/engineers/senior academicians) or for those who are already familiar with the topic (doctoral/postdoctoral scholars). For a beginner or even school/college students, such compilations are bit difficult to access/digest. In fact, they need proper introduction to the topic of conducting polymers including their discovery, preparation, properties, applications and societal impact, using suitable examples and already known principles/knowledge/phenomenon. Further, active participation of readers in terms of “question & answers”, “fill-in-the-blanks”, “numerical” along with suitable answer key is necessary to maintain the interest and to initiate the “thought process”. The readers also need to know about the drawbacks and any hazards of such materials. Therefore, I believe that a comprehensive source on the science/technology of conducting polymers which maintains a link between grass root fundamentals and state-of-the-art R&D is still missing from the open literature.
The first part of the work embodied in this thesis is towards modifying the electronic band-gap of conjugated polymers consisting of thieno[3,4- b]thiophene as one of the repeat units. Two different approaches were undertaken to prepare copolymers of thieno[3,4-b]thiophene in order to accomplish this. First, a simple simultaneous electropolymerization of two monomers from a solution mixture, and second, an oligomeric approach, wherein an oligomer of thiophene and thieno[3,4-b]thiophene with cyanovinylene spacer units was electrochemically polymerized. Several electroanalytical and spectroscopic techniques were used to characterize these polymers. The major part of the thesis is focused on the electrochromic properties of conjugated polymers both in liquid and solid-state electrochemical cells. Several polymers reported in literature were re-evaluated on the basis of its photopic transmissivity. It is necessary that the contrast in a device is more pronounced at wavelengths, wherein the human eye is most sensitive at a given time of the day. At the same time, it is also important to take into account that the eye is sensitive to a broad spectral range. Hence, this photopic approach is very essential in understanding how the intensity of light can be controlled using electrochromic windows. Furthermore, the optical switchability of solid-state electrochromic windows were also studied. Several issues, such as electrodeposition onto indium doped tinoxide (ITO) surfaces with areas ≥ 30cm2, device stability were addressed during the course of this research. The photopically weighted contrast of the device as a whole was found to be enhanced using derivatives of 3,4-propylenedioxythiophene, belonging to the 3,4-alkylenedioxythiophene family. Finally, new device architecture was studied, wherein very low band-gap conjugated polymer with little/no visible electrochromism was used as the ion-storage layer in a dual polymer configuration. Colorimetric analysis of these devices was compared with the earlier devices incorporating a high band-gap anodically coloring conjugated polymer and low band-gap cathodically coloring polymer. These devices were found to be switching between a deep blue to a sky blue, which is a neutral color, as opposed to deep blue to yellow in the earlier configuration. Yellow filter is known to alter the way colors are perceived by the human eye.
This first systematic compilation of synthesis methods for different classes of polymers describes well-tested and reproducible procedures, thus saving time, money and chemicals. Each chapter presents the latest method for a specific class of conjugated polymers with a particular emphasis on the design aspects for organo-electronic applications. In this concise and practically oriented manner, readers are introduced to the strategies of influencing and controlling the polymer properties with respect to their use in the desired device. This style of presentation quickly helps researchers in their daily lab work and prevents them from reinventing the wheel over and over again.
Conjugated polymers hold tremendous potential as low-cost, solution processable materials for electronic applications such organic light-emitting diodes and photovoltaics. While the concerted efforts of many research groups have improved the performance of organic electronic devices to near-relevant levels for commercial exploitation over the last decade, the overall performance of organic light-emitting diode and organic photovoltaic devices still lags behind that of their traditional, inorganic counterparts. Realizing the full potential of organic electronics will require a comprehensive, molecular-level understanding of conjugated polymer photophysics. Studying pure, well-defined, and reproducible conjugated polymer materials should enable these efforts; unfortunately, conjugated polymers are typically synthesized by metal-catalyzed step-growth polycondensation reactions that do not allow for rigorous control over polymer molecular weight or molecular weight distribution (i.e., dispersity). Chain-growth syntheses of conjugated polymers would not only allow for precise control over the aforementioned polymer metrics such as molecular weight and dispersity, but could also potentially create new applications by enabling the preparation of more advanced macromolecular structures such as block copolymers and surface grafted polymers. Our efforts toward realizing these goals as well as toward exploiting chain-growth methodologies to better understand fundamental conjugated polymer photophysics and self-assembly will be presented.
A timely overview of fundamental and advanced topics of conjugated polymer nanostructures Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications is a comprehensive reference on conjugated polymers for energy applications. Distinguished academic and editor Srabanti Ghosh offers readers a broad overview of the synthesis, characterization, and energy-related applications of nanostructures based on conjugated polymers. The book includes novel approaches and presents an interdisciplinary perspective rooted in the interfacing of polymer and synthetic chemistry, materials science, organic chemistry, and analytical chemistry. This book provides complete descriptions of conjugated polymer nanostructures and polymer-based hybrid materials for energy conversion, water splitting, and the degradation of organic pollutants. Photovoltaics, solar cells, and energy storage devices such as supercapacitors, lithium ion battery electrodes, and their associated technologies are discussed, as well. Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications covers both the fundamental topics and the most recent advances in this rapidly developing area, including: The design and characterization of conjugated polymer nanostructures, including the template-free and chemical synthesis of polymer nanostructures Conjugated polymer nanostructures for solar energy conversion and environmental protection, including the use of conjugated polymer-based nanocomposites as photocatalysts Conjugated polymer nanostructures for energy storage, including the use of nanocomposites as electrode materials The presentation of different and novel methods of utilizing conjugated polymer nanostructures for energy applications Perfect for materials scientists, polymer chemists, and physical chemists, Conjugated Polymer Nanostructures for Energy Conversion and Storage Applications also belongs on the bookshelves of organic chemists and any other practicing researchers, academics, or professionals whose work touches on these highly versatile and useful structures.
The synthesis, characterization, and application of conjugated polymer colloidal microspheres are reported. Monodisperse mesoporous silica spheres were utilized as hard templates for the preparation of poly(3,4-ethylenedioxythiophene) (PEDOT)- ilica composites, which could in turn be etched with hydrofluoric acid to yield monodisperse conjugated polymer microparticles. The synthetic procedure was generalized to include other polymers such as polythiophene and poly(N-methylpyrrole). The colloidal and electronic properties of these composites were subsequently studied, and it was found that a balance between colloidal stability and electrical conductivity could be achieved when the mesopores of the silica template were partially filled with polymer. These insights enabled the successful self-assembly of an opaline film of the PEDOT- ilica composite. Bragg diffraction of visible light by the lattice planes of the opal was then demonstrated. The silica host was subsequently explored for its ability to control the phase separation of polymer blends. It was found that depending on the order of polymer addition, phase separation could be suppressed. This resulted in an intimate mixture of the two constituent polymers, and has potential impact in the field of photovoltaics. The colloidal microspheres were also examined for their utility as electrode materials in supercapacitors. The PEDOT microspheres were found to have a mass specific capacitance higher than that of typical electropolymerized PEDOT films, indicating that the morphological control was translated into an improvement in device performance. An ion exchange and in situ polymerization approach was developed in order to incorporate poly(p-phenylenevinylene) into the mesoporous silica template. This yielded a luminescent colloidal material that displayed enhanced optical properties relative to the unencapsulated iii polymer. This is again due to the morphological constraints imposed on the polymer by the mesoporou.
"Conjugated polymers have emerged over the last decades as an intriguing class of electronic materials with potential applications ranging from polymer-based light emitting diodes, sensors, transistors, photovoltaics and many other areas. Despite the development of many useful variants of conjugated polymers, a challenge that remains in this area is their synthesis. All except the most simple conjugated polymers are constructed by a multistep synthesis, where a complex monomer is first assembled prior to polymerization. This not only creates waste with each step, but also makes it challenging to modify polymer structures, as each monomer must be independently prepared. The objective of the research described in this thesis is to develop a new approach to prepare conjugated polymers via multicomponent polymerization reactions. These have provided tunable methods to assemble pyrrole-based conjugated polymers in one pot reactions from combinations of available substrates, such as diimines, diacid chlorides, alkynes and/or alkynes. In addition, these reactions provide access to new classes of conjugated polymers: poly(Münchnones) and poly(phospha-Münchnones). In Chapter 2, we describe the palladium-catalyzed coupling of diimines, diacid chlorides, carbon monoxide and alkynes. This reaction provides access to families of conjugated poly(pyrroles) in one pot reactions, and with independent control of all the substituents and conjugated units. Moreover, a new class of conjugated polymer, a poly(1,3-dipole), can be isolated. The latter exhibits low electronic band-gaps, and can serve as an intermediate in the synthesis of a range of conjugated poly(heterocycles) via 1,3-dipolar cycloadditions. Chapter 3 describes an alternative, phosphonite-mediated multicomponent synthesis of poly(pyrroles). In analogy to the results in Chapter 2, this transformation also uses diimines and diacid chloride monomers, which are in this case coupled by the addition of (catechyl)PPh rather than palladium catalyzed carbonylation. This generates another class of poly(1,3-dipole) that can react with a variety of alkynes or alkenes to form poly(pyrroles). This approach offers several advantages over the one presented in Chapter 2: the polymers exhibit higher molecular weights, it tolerates a broader scope of monomers, and it does not rely on transition metal catalysis. Notably, to the best of our knowledge, this represents the first metal-free multicomponent synthesis of conjugated polymers. In Chapter 4, a new type of donor-acceptor conjugated polymer containing 1,3-dipole units is described: a poly(phospha-Münchnone). These can be isolated from the multicomponent polymerization of diimines, diacid chlorides and (catechyl)PPh presented in Chapter 3. UV-Vis spectroscopy shows that these polymers are low band-gap materials. Moreover, their properties can be easily tuned by choice of the diimine or diacid chloride monomers. In Chapter 5, we studied the use of renewable starting materials in the phosphonite-mediated multicomponent polymerization presented in Chapter 3. The lignin degradation product bis-vanillin is readily incorporated into this platform to generate cross-conjugated polymers, including poly(1,3-dipoles) and poly(pyrroles). Changing the diacid chloride or the alkyne / alkene coupling partner allowed access to a range of polymers with tunable optical properties. 2,5-furandicarboxylic acid (FDCA), a monomer derived from cellulose oxidation, can also be employed as a precursor to the diacid chloride monomer. The latter provides the first example of a conjugated polymer obtained from both components of lignocellulosic biomass." --
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The transformation of nonconjugated polymers into conjugated polymers using elimination reactions is described. Heterocyclic conjugated polymers containing alternating aromatic and quinonoid sections in the main chain are synthesized by chemical or electrochemical redox elimination reaction on soluble precursor polymers containing sp3 carbon atom bridges between the aromatic heterocyclic units. Progress of the redox elimination process is followed by infrared and electronic spectra as well as by cyclic voltammetry. A reaction mechanism in which the precursor polymer undergoes a redox reaction followed by loss of the bridge hydrogens is proposed. The resulting conjugated aromatic/quinonoid polymers generally have very small semiconductor band gaps in accord with predictions of recent theoretical calculations. A brief view of related syntheses of conjugated polymers from nonconjugated precursor polymers is also given.
Conjugated polymers have been the focus of intense research for more than a decade now, and advances in this field are beginning to materialize in the production of high-efficiency opto-electronic materials that may led to the generation of energy without the need for fossil fuels. However, these current materials have not been shown to be capable of reaching efficiency levels high enough to be competitive with the silicon-based solar cells that are the standard today. We embarked on a journey in this work to help the next step in conjugated polymer research be attained. We have done just that through a fundamental study of dilution solution properties of these materials in addition to the synthetic pathway we have cleared so that highly functionalized conjugated polymers may be synthesized that will lead to block copolymers with tailored properties. These materials will revolutionize the field of organic photovoltaics and organic field transistors. The synthetic method for the generation of functionalized conjugated polymers described here represents an approach that can used to impart any number of functionalities onto the conjugated polymer chains which will lead directly to block copolymer systems. We have shown this ability through the synthesis of a diblock copolymer with promise of a miktoarm star block copolymer in this work. The versatility of the method developed here allows for other combinations of polymers and molecular architectures to be attainable in like manner. This work serves to provide other means by which these useful polymers may reach their maximum potential.
The results of a Nobel Symposium on conducting polymers are presented in this volume, which explores the state of the art in electrically conducting organic polymer materials.

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