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Keywords:

  • arylation;
  • conjugation;
  • cross-coupling;
  • electrochemistry;
  • porphyrins

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.