title: Peripheral arylation of subporphyrazines.
abstract: Peripherally hexaarylated subporphyrazines (SubPzs) have been prepared through a Pd-catalyzed, CuTC-mediated coupling of a hexaethylsulfanylated subporphyrazine with arylboronic acids. The introduced aryl substituents strongly influence the electronic properties of the subporphyrazine through effective conjugative interaction. Aryl rings endowed with π-electron-donating groups at the para positions produce a remarkable perturbation of the electron density of the SubPz macrocycle. This is reflected through significant redshifts of the SubPz CT and Q-bands, together with increase of the molar absorptivity of the former, with respect to those exhibited by the hexaphenyl-SubPz 2 a. Moreover, the trend in the first SubPz reduction potentials correlates with the Hammett constants (σp ) corresponding to the para substituents of the aryl. The domed, extended SubPz π-system self-assembles in the solid state to form a dimeric capsule that houses a solvent molecule.
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain.
authors.forename: Tomohiro
authors.initials: T
authors.lastname: Higashino
authors.forename: M Salomé
authors.initials: MS
authors.lastname: Rodríguez-Morgade
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
authors.forename: Tomás
authors.initials: T
authors.lastname: Torres
keywords: arylation; conjugation; cross-coupling; electrochemistry; porphyrins