β-Disubstituted silver(III) corroles: Facile synthesis, photophysical and electrochemical redox properties

Abstract

Facile synthesis of 3,17-disubstituted Ag(III) tritolylcorroles (2-5), R2[TTC]Ag where R = methyl (2), phenyl (3), methyl acrylate (MA) (4) and phenylethynyl (PE) (5) using Pd-catalyzed reactions in good to excellent yields are reported. All synthesized corroles were characterized by various spectroscopic techniques and mass spectrometry. MA2[TTC]Ag (4) and PE2[TTC]Ag (5) exhibited highly red-shifted electronic spectral bands with considerable broadening due to extended [Formula: see text]-conjugation and electron withdrawing effect of [Formula: see text]-substituents. Geometry optimization of these corroles was performed using density functional theory (DFT). Among all, MA2[TTC]Ag (4) exhibited very high dipole moment (10.31 D) which could be the potential candidate for nonlinear optical (NLO) applications. The redox tunability was achieved by substituting electron donating and withdrawing substituents at the [Formula: see text]-positions. Particularly, corroles 4 and 5 exhibited lower HOMO–LUMO gap due to extended [Formula: see text]-conjugation and electron withdrawing [Formula: see text]-substituents.