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

Facile synthesis of 3,17-disubstituted Ag(III) tritolykorroles (2-5), R-2[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. MA(2)[TTC]Ag (4) and PE2[TFC]Ag (5) exhibited highly red-shifted electronic spectral bands with considerable broadening due to extended pi-conjugation and electron withdrawing effect of beta-substituents. Geometry optimization of these corroles was performed using density functional theory (DFT). Among all, MA(2)[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 beta-positions. Particularly, corroles 4 and 5 exhibited lower HOMO-LUMO gap due to extended pi-conjugation and electron withdrawing beta-substituents.

Automated summary

A series of 3,17-disubstituted Ag(III) tritolykorroles were synthesized in good to excellent yields using Pd-catalyzed reactions. Among them, MA(2)[TTC]Ag (4) showed potential for nonlinear optical applications due to its high dipole moment. Redox tunability and lower HOMO-LUMO gap were achieved through substituting electron donating and withdrawing groups at the beta-positions.