Metal-mediated linear self-assembly of porphyrins

Porphyrin derivatives are highly relevant to biological processes such as light harvesting and charge separation. Their aromatic electronic structure and their accessible HOMO−LUMO gap render porphyrins highly attractive for the development of opto- and electro-active materials. Due to the often difficult covalent synthesis of multiporphyrins, self-assembly using metal complexation as the driving force can lead to well defined objects exhibiting a controlled morphology, which will be required to analyse and understand the electronic properties of porphyrin wires. This article presents two assembly approaches, namely by peripheral coordination or by binding to a metal ion in the porphyrin core, that are efficient and well designed for future developments requiring interactions with a surface

Improved preparation deoxophylloerythroetioporphyrin (DPEP) and its 15′-methyl derivative from chlorophyll a.

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Peripherally Metallated Porphyrin Derivatives : Approaches and Properties

During the last 15 years, the synthetic modifications of porphyrins and porphyrazines have evolved rapidly. Despite this progress, the chemistry of porphyrinoids bearing coordination complexes or organometallic fragments at their periphery is still much less developed than the coordination chemistry using the apical positions of the central metal ions or remote coordination sites. The two latter types of coordination chemistry are much easier to perform from a synthetic point of view. However, transition metal-based synthetic chemistry is improving rapidly, allowing the introduction of functionalities, mainly heteroatoms or boron derivatives, at the periphery of aromatic rings. The coordination chemistry or organometallic chemistry that links together two large porphyrinoids while simultaneously allowing large electronic or magnetic interactions between these macrocycles is still limited to a few examples. The synthesis of di- or polyfunctionalized porphyrins must be developed. The inorganic chemistry around the metal ion linkages also needs to be improved and varied to give new compounds with potentially new properties. Finally, once the molecular chemistry is well understood, the chemistry of new molecular materials will need to be developed toward polymeric species

Unexpected methylation and propylation of porphyrin E-ring during the hemisynthesis of deoxophylloerythroetioporphyrin (DPEP)

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Synthesis, structural characterization, and electrochemical studies of nickel porphyrins bearing two peripheral conjugated chelating groups

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Synthesis of extended porphyrins by connection of meso-aryl groups with beta-pyrrolic positions

International audienceThis review focuses on synthetic strategies leading to extended porphyrins, but is limited to examples in which at least one b-pyrrolic carbon is linked to a meso-aryl substituent. Friedel-Crafts reactions are covered first because historically they were the first reactions employed to link b-pyrrolic carbons with meso-aryl groups, thus creating new six-membered fused rings. Other reactions inserting heteroatoms follow. Direct cyclizations between an ortho-carbon and a b-pyrrolic position are presented next. Finally, new highly extended chromophores are described. These compounds are generally obtained in two consecutive reactions. First a Suzuki coupling is used to introduce an aryl group in one or two mesopositions. Then the new fused rings are generated by oxidative cyclizations

New dyads using (metallo)porphyrins as ancillary ligands in polypyridine ruthenium complexes. Synthesis and electronic properties

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Ground and Excited State Properties of New Porphyrin Based Dyads: A Combined Theoretical and Experimental Study.

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