Post Synthetic Modification of Planar Antiaromatic Hexaphyrin (1.0.1.0.1.0) by Regio-Selective, Sequential SNAr

In spite of unique structural, spectroscopic and redox properties, the synthetic variants of the planar, antiaromatic hexaphyrin (1.0.1.0.1.0) derivatives 2, has been limited due to the low yields and difficulty in access to the starting material. A chemical modification of the meso-substituents could be good alternative overcoming the synthetic barrier. Herein, we report a regio-selective nucleophilic aromatic substitution (SNAr) of meso-pentafluorophenyl group in rosarrin 2 with catechol. The reaction afforded benzodioxane fused rosarrin 3 as single product with high yield. The intrinsic antiaromatic character of the starting rosarrin 2 retained throughout the reactions. Clean, two electron reduction was achieved by treatment of 3 with SnCl2 center dot 2H(2)O affording 26 pi-electron aromatic rosarrin 4. The synthesized compounds exhibited noticeable changes in photophysical and redox properties compared with starting rosarrin 2.

Automated summary

This study modified the synthesis of antiaromatic hexaphyrin derivatives by chemically altering the meso-substituents, resulting in high-yield reaction products. A regio-selective nucleophilic aromatic substitution led to the successful synthesis of a compound with 26 pi-electron aromaticity, showing significant changes in photophysical and redox properties compared to the starting material.