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 Porphyrins, Volume I: Structure and Synthesis, Part Ais the first in a series of seven volumes and covers topics like nomenclature, purification, and structural determination of porphyrins, metalloporphyrins, and other related compounds. This volume serves to be a critical review of the topics covered and presents a complete and comprehensible discussion on the chemistry and biochemistry of porphyrins. The chapters in the text tackle the history and geochemistry of porphyrins and related systems. Also covered and discussed in the chapters is the synthesis of porphyrins from mono-, di-, and tetrapyrrolic intermediates. The isolation and modification of porphyrins from natural sources are also discussed. Other related compounds are also included, such as metallo-, aza-, and N-methylporphyrins, and their synthesis and properties. This book is a good introduction and reference for students studying in the fields of chemistry and biochemistry.

The Porphyrins, Volume II: Structure and Synthesis, Part B is devoted to the structure and synthesis of porphyrins, their precursors, catabolic derivatives, and related systems. The book also covers nomenclature, history, geochemistry, purification, and structural determination of porphyrins, metalloporphyrins, and mono- and polypyrrolic compounds. This volume is organized into 10 chapters and begins with an overview of hydroporphyrins, paying particular attention to their synthesis and stereochemistry as well as reactivity, spectroscopy, and analogues. This book then discusses the synthesis, properties, thermodynamic stability, and evolution of porphyrinogens. The following chapters focus on porphyrins reversibly modified at the periphery by oxidation (oxophlorins) and by irreversible reactions at the periphery. The synthesis of photoexcited porphyrins, metalloporphyrins, and chlorophylls is covered. In addition, chapters on linear polypyrroles, their metal complexes, and macrocycles other than porphyrins are included. This book should be useful to inorganic, organic, physical, and biochemists interested in porphyrin chemistry and biochemistry.

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.

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.

This thesis begins with an introduction to porphyrins and chlorins, their natural and synthetic analogues, the biological roles of porphyrins, followed by the synthesis of porphyrins and their derivatization towards chlorins. The introduction also deals with the structural analysis of porphyrins and a classification of their optical spectra, followed by a brief outline of the applications of porphyrins and chlorins. Subsequently, there is a discussion on the various types of porphyrins present with substitution in the porphyrin core as well as in the periphery. The structure, synthesis and spectroscopic properties of core substituted and peripherally modified porphyrins are also discussed. A detailed description of porphyrin and chlorin N-oxides is carried out in the Results and Discussion Chapter 1, describing their synthesis, reactivity, crystal structure and a comparison of their optical spectra. A possible biological application is outlined. An exploration of the reactivity of the porphyrin α-position and synthesis of a pyrrole-ring contracted chlorin is discussed in Chapter 2. In Results and Discussion Chapter 3, the synthesis, spectroscopy and stereochemical assignment of helimeric porphyrinoids with a morpholino subunit are discussed. In Results and Discussion Chapter 4, the synthesis of trans-diolchlorins and their manipulation leading up to the synthesis of pyrrole ring homologated porphyrins is discussed.