Push–pull type manganese(III)corroles: Synthesis, electronic structures and tunable interactions with ctDNA

Abstract

ABSTRACT:The synthesis of three low symmetry A 2 B type Mn(III)triarylcorroles with mesoaryl substituents that provide push-pull electrondonating and withdrawing properties is reported. An analysis of the structureproperty relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A 2 B type Mn(III)triarylcorroles interact strongly with cellfree circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electrondonating substituent is introduced at the 10position of the mesotriarylcorrole ligand.

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

“…The acid-catalyzed condensation of dipyrromethane 13 with the appropriate aldehyde followed by oxidation with p -chloranil gave corroles 14 . The reaction of these macrocycles with manganese chloride in DMF afforded metallocorroles 15a – c in high yields (63–90%) [ 39 ]. The fluorescence studies reveal that Mn(III) corroles 15a – c strongly interact with the cell-free circulating tumor DNA in solution and the ability of this interaction increases with the electron-donating character of the 10-substituent of the triarylcorrole.…”

Corroles at work: a small macrocycle for great applications

“…98 Push-pull manganese corrole complexes. 277 interaction was observed only at low concentration, while at higher concentration the iron dimer complex mainly stacks in the major grooves of CT-DNA. 205 Push-pull manganese(III) corroles bearing -NO 2 EWG at the 5,15-meso-positions and different EDG at the 10-meso-position (e.g.…”

“…Interestingly, the strength of the interaction can be increased when a stronger EDG group is introduced at the 10-meso-position. 277 Very recently, the photocatalytic tetra-thiocyanation of freebase corroles using ammonium thiocyanate was reported (Fig. 99).…”