Synthesis and Properties of meso-Arylated Corrphycenes

Abstract

A novel synthetic procedure for meso-aryl-substituted corrphycenes has been developed. Suzuki-Miyaura coupling of α,α'-dibromodipyrrin with vic-diborylalkene and o-diborylbenzene afforded ethenylene- and phenylene-bridged bisdipyrrins, respectively, which were transformed to the corresponding corrphycenes upon treatment with palladium acetate. The bridging units significantly affect the macrocyclic π-conjugation circuits, thus changing the aromatic characters and absorption features of corrphycenes.

Synthesis of Phlorin Analogues of Dithiacorrphycene and Their Use as Specific Chemodosimetric Sensors for Fe3+ Ions

“…[16] For example, the N 4 core geometry is gies and instability,o wing to lower symmetry. [10,[23][24][25] The properties of porphyrin isomersc an be furtheralteredbym odifying the N 4 core. [26] Replacemento fo ne or two pyrrole nitrogen atom(s) of porphyrins by other donora toms,s uch as oxygen, sulfur,s elenium, and tellurium, leads to new porphyrin analogues referred to as core-modified or heteroatom-substituted porphyrins.…”

“…Studies have shown that porphycenes, which are better investigated among porphyrin isomers, are very promising as phototherapeutic agents in photodynamic therapy . Interestingly, except porphycenes, the other structural isomers of porphyrins, such as corrphycene, hemiporphycene, and isoporphycene, have not been investigated to a greater extent because of their less developed synthetic methodologies and instability, owing to lower symmetry . The properties of porphyrin isomers can be further altered by modifying the N 4 core .…”

Bis(naphthobipyrrolyl)methene-derived hexapyrrolic BODIPY as a single-molecule helicate with near-infrared emission

“…17 In this regard, we were interested in determining the effect of β,β ′-bipyrrole fusion on the chemistry of corrphycene, another closely related isomer of porphyrin. 18 However, synthesis of the precursor tetrapyrrole having the naphthobipyrrole moiety from the corresponding dialdehyde eluded us (Scheme S1, ESI‡). Therefore, we redesigned our approach to synthesize the desired tetrapyrrole derivative by carrying out an acid-catalysed condensation of naphthobipyrrole IV with the acetoxypyrrole V .…”