Kinetic versus Thermodynamic Control Over Multiple Conformations of Di‐2,7‐naphthihexaphyrin(1.1.1.1.1.1)

Abstract

rating two built-in 2,7-naphthylene moieties was synthesized as two separate,c onformationally locked stereoisomers.B oth conformers followed complex protonation pathwaysinvolving structurally different species,w hich can be targeted under kinetic and thermodynamic control. The neutralization of the ultimate dicationic product, accessible from both stereoisomers of the free base,allowed to realizethe complex conformational switching cycle involving six structurally different species.

The Intracavity Extension of 28-Hetero-2,7-naphthiporphyrins in Reactions with Alkylamines

“…10−12 Recently, we have demonstrated that the horizontal expansion of the m-benziporphyrin 13,14 framework could provide the 28-hetero-2,7-naphthiporphyrins 1-X (X = S, Se, Te), which act as macrocyclic ligands for phosphorus-(V). 15,16 The carbaporphyrinoid macrocycles, aside from their role as unusual ligands in coordination and organometallic chemistry, often enable peculiar reactivity within the macrocyclic cavity. 2 Although the core chemistry of N-confused porphyrin, 17,18 the archetypical carbaporphyrinoid, is very well documented, 19 other carbaporphyrinoids are much less studied in this context despite the fact that they were shown to undergo remarkable transformations.…”