Document from the year 2020 in the subject Chemistry - Macromolecular Chemistry, Polymer Chemistry, grade: 2, , language: English, abstract: This work gives an overview over core modified Porphyrinoids. Specifically: Smaragdyrins, Expanded Porphyrinoids and Corroles. It does so by, in two chapters, defining each of the aforementioned chemical combinations ́ synthesis and characterization, properties and respective dyads. Smaragdyrin is a pentapyrrolic 22π-electron expanded porphyrin system bearing two direct pyrrole-pyrrole bonds. This macrocycle and its core modified derivative i.e. 25-oxasmaragdyrin have received upsurge interest in recent years due to their notable optical and electrochemical properties. Corroles are aromatic tetrapyrrolic macrocycles containing one meso carbon less compared to porphyrins and have one direct pyrrole-pyrrole linkage. This class of macrocycle possesses novel spectral, electrochemical and luminescence properties that can be exploited in material applications. In this book, we have discussed the synthesis, properties and their limited coordination chemistry of expanded porphyrinoid 25-oxasmaragdyrin and core-modified corroles. Corroles, on the other hand, are tetrapyrrolic contracted porphyrins, fully conjugated 18π electron macrocyles containing three methine bridges and one direct pyrrole-pyrrole linkage.

FUNDAMENTALS OF PORPHYRIN CHEMISTRY An indispensable and concise overview of the chemistry of porphyrins and related molecules In Fundamentals of Porphyrin Chemistry: A 21st Century Approach, a team of distinguished researchers delivers a compact and accessible introduction to the broad field of porphyrin chemistry. It discusses the basics of porphyrin synthesis and structure, as well as that of related molecules, and the current and future roles that porphyrins play in chemical transformations, materials design and synthesis, energy capture and transduction, human health, and the environment. This edited volume is a self-contained tutorial on concepts of critical importance to porphyrin chemistry and serves as the foundation for discussions about the applications of porphyrin-related compounds found in the second volume. This book contains: A thorough introduction to porphyrins, including their structure, nomenclature, naturally occurring porphyrins, synthetic porphyrins, and common families of porphyrin-related compounds Comprehensive explorations of chemical porphyrin synthesis, including how to synthesize porphyrins from simple, symmetric, and advanced ABCD-substituted porphyrins Practical discussions of the physical characteristics of porphyrins, including their structural features, electronic structure, spectroscopy, magnetism, electrochemistry, and electron transfer processes Perfect for experienced academic researchers in the field of porphyrin chemistry seeking a quick reference, Fundamentals of Porphyrin Chemistry: A 21st Century Approach is also an indispensable resource for researchers new to the field who need an overview directing them to literature in more focused areas.

Chapter headings: Introduction. Contracted Porphyrins. Isomeric Porphyrins. Expanded Porphyrins Containing Four Pyrroles. Contracted Expanded Porphyrins: Sapphyrins and Smaragdyrins. Other Carbon-bridged Pentapyrrolic Systems. Carbon-linked Hexapyrrolic Systems and Heteroatom Analogues. Higher Order Systems. Nitrogen-Bridged Expanded Porphyrins. ApplicationsIntroduction -- Contracted porphyrins -- Isomeric porphyrins -- Expanded porphyrins containing four pyrroles -- Contracted expanded porphyrins: sapphyrins and smaragdyrins -- Other carbon-bridged pentapyrrolic systems -- Carbon-linked hexapyrrolic systems and heteroatom analogs -- Higher order systems -- Nitrogen-bridged expanded porphyrins -- Applications -- Index.

The thesis proposes to refine and extend the 'porphyrin breaking and mending' methodology, to modify known and novel pyrrole-modified porphyrins (PMPs), to evaluate their (photo)physical properties in theory and experiment, and to explore - alone and in collaboration with specialty groups - their applications. The investigations were carried out such that the steric (e.g., ring-size of the non-pyrrolic heterocycle; beta-to-ortho-phenyl linkages) and electronic influences (e.g., degree of saturation of the macrocycle, nature of functional groups) of the modifications on the physical properties of the PMPs could be delineated. The reaction of beta-octaalkylporphyrins (octaethylporphyrin and etioporphyrin I) with ozone to generate chlorin-like chromophores was studied. Such a reaction was described firstly over 80 years ago but was not understood at the time. The work expands on the knowledge of converting porphyrins to porphyrinoids containing non-pyrrolic heterocycles of potential utility. We introduce novel methodologies toward the synthesis of porphyrinoids carrying beta-to-ortho-phenyl fusions and expand on the scope and limits of the chemistry and interconversion of pyrrole-modified porphyrins. The macrocycle conformation of [meso-tetraarylporphyrinato] metal complexes is metal-dependent. Furthermore, hydroporphyrins and some of their analogues are known to be more conformationally flexible than the parent porphyrins, but the extent to which this is reflected in their metal-dependent conformations was much less studied. Therefore, their conformations were determined using X-ray crystal structure diffractometry and compared against those of their free bases, as well as against the conformations of the corresponding metalloporphyrins to further define the conformational and electronic effects governing pyrrole-modified porphyrins.

Paperback. The porphyrins are a class of naturally-occurring macrocycles and are ubiquitous in our world. As such, they have been called the Pigments of Life. This auspicious designation reflects their importance in numerous biological functions. Indeed, life as we understand it relies on the full range of biological processes that are either performed by or catalyzed by porphyrin-containing proteins. Chlorophyll-containing photosynthetic reaction centers in plants, for instance, convert light energy into chemical energy while producing oxygen along the way. It is this oxygen, evolved from photosynthesis, that is transported, stored, and reduced by heme-containing proteins in many organisms, including mammals. Not surprisingly, therefore, these molecules remain of fundamental interest to chemists and biochemists. Indeed, they continue to be intensely investigated by researchers world-wide.Inspired by the importance of the porphyrins, a new research di

The McMurry Reaction in Porphyrinoid Chemistry, by Kevin M. Smith Meso-tetraarylporphyrins: synthetic strategies and reactivity profiles based on nitro/amino substituents, by Maria da Graça Neves Functionalization of corroles, by José Cavaleiro Degradation pathways for porphyrinoids, by Jacek Wojaczynski Synthetic routes to porphyrinoids, by Sara Nardis Recent developments of non covalent porphyrin assemblies, by Donato Monti

The Chemistry and Biology of Nitroxyl (HNO) provides first-of-its-kind coverage of the intriguing biologically active molecule called nitroxyl, or azanone per IUPAC nomenclature, which has been traditionally elusive due to its intrinsically high reactivity. This useful resource provides the scientific basis to understand the chemistry, biology, and technical aspects needed to deal with HNO. Building on two decades of nitric oxide and nitroxyl research, the editors and authors have created an indispensable guide for investigators across a wide variety of areas of chemistry (inorganic, organic, organometallic, biochemistry, physical, and analytical); biology (molecular, cellular, physiological, and enzymology); pharmacy; and medicine. This book begins by exploring the unique molecule’s structure and reactivity, including important reactions with small molecules, thiols, porphyrins, and key proteins, before discussing chemical and biological sources of nitroxyl. Advanced chapters discuss methods for both trapping and detecting nitroxyl by spectroscopy, electrochemistry, and fluorescent inorganic cellular probing. Expanding on the compound’s foundational chemistry, this book then explores its molecular physiology to offer insight into its biological implications, pharmacological effects, and practical issues. Presents the first book on HNO (nitroxyl or azanone), an increasingly important molecule in biochemistry and pharmaceutical research Provides a valuable coverage of HNO’s chemical structure and significant reactions, including practical guidance on working with this highly reactive molecule Contains high quality content from recognized experts in both industry and academia