Expanded Porphyrins: More Confusion All the Time

Abstract

Confusion leads to cooperative reactivity: Oxidative ring‐closure reactions of oligopyrranes containing two terminal confused pyrroles yield expanded porphyrinoids, which show cooperative reactivity between the directly linked confused pyrroles. These transformations constitute a new method for the synthesis of novel porphyrinoids with unconventional pyrrole linking modes and unique properties.

Strongly Coupled Oxasmaragdyrin–BF2 Chelated Dipyrrin Dyads: Syntheses, X‐ray Structure, Ground‐ and Excited‐State Charge‐Transfer Interactions

“…In recent years, chemistry of structural isomers of tetrapyrroles, expanded porphyrins, and core modified porphyrins has attracted considerable attention, especially from the synthetic chemist community . Some of these hetero‐macrocyclic compounds are known for their strong absorption and emission, and useful redox properties, thus making them useful materials for building light‐energy‐harvesting systems.…”

“…In recent years, chemistry of structural isomerso ft etrapyrroles, expandedp orphyrins, andc ore modified porphyrins has attractedc onsiderable attention, especially from the synthetic chemistc ommunity. [39][40][41][42][43][44][45][46] Some of these hetero-macrocyclic compounds are known for their strong absorption and emission, and useful redox properties, thus making them useful materials for buildingl ight-energy-harvestings ystems. Among such molecular systems, smaragdyrin, a2 2-p electron aromatic macrocycle containing five pyrroles or mixed five-membered heterocycles connected through three methine bridges and two direct bonds are known to possess very novel spectral and electrochemical features.…”

Carbaporphyrinoid Systems

“…Therefore, the definitions of expanded carbaporphyrinoid systems become blurred and possibly meaningless with regard to these types of structures. While a full discussion of expanded porphyrins lies outside of the scope of this review, − selected examples are provided. In an early study, meso -tetraphenylsapphyrin 787 was shown to favor an inverted pyrrolic subunit (Scheme ), although protonation led to the formation of a dication with a pentaaza cavity .…”

Porphyrins and Phthalocyanines on Solid-State Mesoporous Matrices as Catalysts in Oxidation Reactions

“…Similarly, heme is crucial for living organisms, as it is responsible for storage and transport of oxygen, and it also forms an active center of cytochrome P-450 [ 2 , 3 ]. Apart from porphyrins there are other numerous synthetic tetrapyrrole macrocycles, such as phthalocyanines (Pcs), chlorins, corroles and porphyrazines [ 4 , 5 , 6 , 7 ]. Applications of porphyrins, phthalocyanines and related macrocycles are intensively studied in many fields.…”