Highly reactive meso-like positions of dipyrihexaphyrin

Abstract

The meso-like position of a pyridine-containing porphyrin analogue structurally related to amethyrin was found to be highly reactive to undergo addition of alcohols, amines and hydrogen cyanide at room temperature under neutral conditions.

Benzene- and pyridine-incorporated octaphyrins with different coordination modes toward two PdII centers

“…Pyridine-modified rubyrin 6 underwent protonation-induced flipping of the pyridine subunits 17 , and cyclo [6]pyridine [6]pyrrole 7 was synthesized as the largest pyridine-incorporating expanded porphyrin that showed characteristic conformational flexibility (Fig. 1) [14][15][16][17][18][19][20][21][22][23] .…”

UO22+-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex

“…A recent example by Osuka and co-workers demonstrated that water can insert into the meso -position of hexaphyrin (1.1.1.1.1.1) upon Cu( ii )- or Ni( ii )-metallation 32. Setsune and co-workers have also reported that dipyriamethyrin can undergo meso -selective nucleophilic addition with cyanide, amines, and alkoxides 33. Elegant demonstrations of ring contraction have been observed by the Furuta group with N -confused dihydrosapphyrin to give neo -confused corrole,34 as well as by Maruyama, Fujita, Osuka, and co-workers with bis-Cu( ii )octaphyrin to give Cu( ii )-porphyrin 35.…”

Bipyricorrole: A Corrole Homologue with a Monoanionic Core as a Fluorescence ZnII Sensor

“…Since then, several pyridyl derivatives have been reported, including pyriporphyrin ( 2 ) and its Zn II ( 2 a ) and Fe III complexes, confused pyriporphyrin– and its Fe II , Fe III ,– and Pd II complexes, oxypyriporphyin– and its Ni II[6e] and Fe III[6f] complexes, and a dipyridinoid‐substituted porphyrin derivative. Similarly, a variety of pyridine‐based derivatives have been described and characterized: (i) expanded porphyrins, such as 12‐hydroxypyrisapphyrin, dipyrihexaphyrin,– tetrapyrioctaphyrin, bipyrioctaphyrin, and cyclo[ m ]pyridine[ n ]pyrroles; (ii) phathalocyanine derivatives such as hemiporphyrazines; (iii) calixpyrrole derivatives such as meso ‐octaethyl calix[4]pyridine; and (iv) cryptand‐like pyriporphyrinoid macrocycles . Recently, a series of porphyrin‐related macrocycles with N4 coordination spheres were reported, including: 1,10‐phenanthroline‐embedded porphyrins ( 3 ) as Mg II sensors; carbazole and pyridine building blocks with high‐spin Co II complexes; and cobalt(II) phenanthroline‐indole macrocycles as electrocatalysts for oxygen reduction .…”