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The work contained within this thesis explores the synthetic strategies to several novel conjugated systems derived from porphyrin, NDI and TTF building blocks and their subsequent characterasation. These novel compounds have applicability in studying the factors that govern ET and EnT in interesting redox processes and as sensors. The bulk of research undertaken utilises the easy to prepare porphyrin-dione 44 and TTF 78 as well as tetrabromo NDI 19. Chapter 1 provides an introduction to the motivation for this research. The Chapter also summarises major directions in the fields of porphyrin, NDI and TTF chemistry and defines the significance and role of their properties as well as relevant applications.Chapter 2 explores the synthesis of novel porphyrinogens including oxidation of the porphyrin macrocycle. Core to the strategy is the porphyrin-dione 44. From this dione, porphyrin anhydride 57 and related metallo-porphyrins are synthesised and their physical properties explored. Obtaining porphyrin-lactone 58 as a side product during these reactions led us to synthesis novel lactams 62 and 63. Reaction of porphyrin-lactone 58 with hydrazine-hydrate converts the lactone moiety to an N-aminolactam 62. It also chemically reduces the antipodal pyrrolic moiety in the N-aminolactam, producing the chlorin-like N-aminochlorolactam 63 as well. This lactone-to-lactam replacement does not dramatically change the UV-visible spectroscopic properties of the N-aminolactam 62, however N-aminochlorolactam 63 shows intense Q band at 696 nm, which is larger than that of either of porphyrin-lactone 58 or N-amino-porpholactam 62, and is also shifted to the red region. Chapter 3 investigates the synthesis of novel porphyrin-TTF systems and their metal complexes. A tetrathiafulvalene donor has been annulated to 44 via quinoxaline linkers to form a novel asymmetric dyad 79. Chemical and physical properties are also outlined by utilising different methods such as UV-visible spectroscopy, fluorescence spectroscopy and cyclic voltammetry. These extended [pi]-conjugated molecules absorb light over a wide region of the UV-visible spectrum. Preliminary fluorescence testing of these compounds suggests that electron and/or energy transfer processes take place from the TTF unit as a donor to the porphyrin moiety as an acceptor. Also, cyclic voltametric studies allow the differentiate between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these compounds. X-ray crystallography was used to characterise compound 79, adding to the structural information gained through other characterisation techniques.Chapter 4 investigates the synthesis of a new naphthalene diimide 104, in which a TTF donor has been attached to the naphthalene diimide core via a rigid bridge. The electronic properties of 104 are studied in detail. A strong electronic absorption profile extends far into the visible spectral region, which originates from its inherent electronic donor-acceptor nature. Also, the presence of a strong absorption at 1270 nm upon chemical oxidation, confirms significant [pi]-[pi] interactions in the compound due to aggregation.The work presented in Chapter 5 focused on synthesising of a novel 2,3-dipyrrol-2'-yl-TTF-quinoxaline 123, which is highly selective and sensitive for F- with detection possible by both colorimetric and fluorometric analyses. The target compound 123 was obtained via the direct condensation reaction of 78 with the 2,3-dipyrrol-2'-yl ethanedione 121 in good yield, and then characterized by various methods including X-ray crystallography. The UV-visible spectrum of 123 in DCM shows three strong absorption bands, which change after the addition of fluoride ion. Compound 123 also shows an emission intensity enhancement with slight red shift upon addition of F-, while no significant changes in the spectra of 123 was observed upon addition of AcO-, H2PO4-, Cl-, Br- and HSO4- in the same solvent. Chapter 6 reflects on the work undertaken in Chapters 2-5 and comments on future directions. It also describes some ancillary works to the main themes of this thesis. Synthesis of the NDI-TTF annulated compounds 126 and 127 under mild conditions are detailed, as well as dimer 128, which might have interesting photophysical properties. A new trimer 130 was also synthesised.
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.
Organic Chemistry provides a comprehensive discussion of the basic principles of organic chemistry in their relation to a host of other fields in both physical and biological sciences. This book is written based on the premise that there are no shortcuts in organic chemistry, and that understanding and mastery cannot be achieved without devoting adequate time and attention to the theories and concepts of the discipline. It lays emphasis on connecting the basic principles of organic chemistry to real world challenges that require analysis, not just recall. This text covers topics ranging from structure and bonding in organic compounds to functional groups and their properties; identification of functional groups by infrared spectroscopy; organic reaction mechanisms; structures and reactions of alkanes and cycloalkanes; nucleophilic substitution and elimination reactions; conjugated alkenes and allylic systems; electrophilic aromatic substitution; carboxylic acids; and synthetic polymers. Throughout the book, principles logically evolve from one to the next, from the simplest to the most complex examples, with abundant connections between the text and real world applications. There are extensive examples of biological relevance, along with a chapter on organometallic chemistry not found in other standard references. This book will be of interest to chemists, life scientists, food scientists, pharmacists, and students in the physical and life sciences. Contains extensive examples of biological relevance Includes an important chapter on organometallic chemistry not found in other standard references Extended, illustrated glossary Appendices on thermodynamics, kinetics, and transition state theory
Filling a gap in the chemical literature, this monograph provides a comprehensive overview of the fascinating and expanding field of cross-conjugated molecules, their chemistry, synthesis and properties. The editors are world leading scientists in the field, and have assembled a team of experts to discuss different classes of cross-conjuagted molecules, as well as the use of cross-conjugation for organic synthesis and applications in electronic systems and material science.
First published in 1997. Routledge is an imprint of Taylor & Francis, an informa company.
Synthesis of several interrelated metallo-compounds is described. They are of intrinsic interest in their own right and were designed as intermediates and model studies for construction of various acetylene metal systems with interesting synthetic and optical potential. Synthesis of a triacetal and its eta6-tricarbonylchromium(0) complex 31 is described. Further transformations towards an eneyne derivative of 31 were complicated by the inherent instability of the complex towards oxidative decomplexation. Synthesis of a series of hexa-substituted eta 6-tricarbonylchromium(0) complexes 39--47 (E = H, Me, SiMe3, SnMe3, Cl, Br, I, COH, CO2Me) and 54--57 (E = H, Cl, Br, I) by di- or tri-lithiation of the parent compounds followed by quenching with a series of electrophiles is reported. Attempts to obtain alkynylated derivatives of the complexes by Sonagashira coupling reactions failed to produce the desired products. A novel tridurylborane 83, incorporating three azulenyl substituents, was prepared and displayed unique photophysical properties with an absorption maximum nearly 80 nm longer than that of its precursor. A new class of heteroatom-containing triarylboranes 79 (R = OMe) and 96 (R = Me) were synthesized. Triarylborane 96 displayed broadened resonances in the 1H NMR spectrum at room temperature and a low-temperature 1H NMR study revealed that the borane existed as an approximate 10:1 ratio of two enantiomeric sets of conformational isomers. Triarylborane 96 was further extended by sequential Sonagashira coupling reactions to yield the highly fluorescent chromophore 110, which exhibited intense and long-wave absorption and emission maxima.