Chemical transformation of doubly N-confused porphodimethenes to variants of (anti)aromatic doubly N-confused porphyrinoids and σ-aromatic doubly N-confused isophlorinoids

Abstract

Chemical conversion of non-aromatic trans-doubly N-confused porphodimethene to hitherto unknown variants of doubly N-confused porphyrinoids/isophlorinoid have been unravelled by precise interplay between the types of oxidants, the types of meso-aryl...

21-Carba-23-oxaporphyrinoids and 21-oxo-21-carba-23-oxaporphyrinoids: macrocyclic π-conjugation involving the carbonyl moiety

“…This substituent increases the number of accessible protonation sites and can participate in the tautomerism of the whole molecule. Furthermore, the controlled tautomeric enol-ketone-like equilibria can function, at least in principle, as aromaticity switching mode as reported for pairs of hydroxy/oxo derivatives of benziporphyrin, 31,32 N-confused porphyrin 8 , 33 doubly N-confused isophlorin 9 , 34 azuliporphyrin 10 , 35–37 and benzocarbaheteroporphyrin 11 38 (Chart 2).…”

Organometallic chemistry confined within a porphyrin-like framework

“…By using DDQ instead of chloranil for oxidation, the tetraoxygenated product S99-3 is formed instead of S99-1. 225 Incorporation of five-membered rings -cyclopentadiene and fused derivatives Simple building blocks, including those incorporating azulene, indene, or cyclopentadiene, were used as the rewarding units to construct cis-or trans-dicarbaporphyrins. A first example is bsubstituted cis-diazuliporphyrins S100-1 (Scheme 100) which also accounts for the first case of mesoionic porphyrinoid.…”

“…By using DDQ instead of chloranil for oxidation, the tetraoxygenated product S99-3 is formed instead of S99-1 . 225…”

Rational and controllable syntheses of variants of modified N-confused N-fused porphodimethenes and a porphotrimethene with adaptive properties

“…13 Anion-induced deprotonation as the basis of anion sensing has been demonstrated by Fabbrizzi and co-workers. 14 Within the context of the generalized extended porphyrin and isomeric porphyrin paradigm, 15 the most challenging artificial structural analogues are N-confused porphyrins (NCPs) 16,17 and N-fused porphyrins, 18 which have been discovered and a plethora of unusual coordination complexes have been described. 19 In contrast to porphyrin, NCPs, displaying an outward-pointing NH group viable as a potential site for anion binding, exhibited significant affinity towards halide ions due to effective hydrogen bonding between the outer NH group of NCPs and halide ions.…”