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

Retrosynthetic design and synthesis with structural isolation of two unprecedented core modified N-confused N-fused porphodimethene-like porphyrinoids possessing a [5.5.5.5] tetracyclic ring with tunable photophysical properties is reported. The solid-state X-ray crystal structure reveals the expected cis geometry for the meso-sp3 carbons. Controlled chemical oxidation of the porphodimethene analogue 11 bearing the N-confused pyrrole moiety to the corresponding porphotrimethene 12 has been achieved in quantitative yield, while 10 bearing the N-methyl N-confused pyrrole moiety remained unsusceptible to chemical oxidation. All three S2N3 hybrid N-confused N-fused porphodi(tri)methene-like porphyrinoids 10-12 could recognize the fluoride anion with high selectivity; however, porphodimethene 10 and porphotrimethene 12 do so via deprotonation rather than an anion recognition based mechanism as has been anticipated in the case of porphodimethene 11. Striking compromise between flexibility and rigidity via built-in fused tetra pentacyclic moiety (5.5.5.5): Highly stable meso-aryl substituted core modified N-confused N-fused calix[4]phyrin analogues as selective fluoride ion receptors via deprotonation and/or anion recognition mechanism.