# Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators

## TL;DR

This paper explores how Ni(II) norcorroles react with azo radical initiators to form new bowl-shaped structures with unique properties.

## Contribution

The study reveals a novel radical reactivity pattern of Ni(II) norcorroles at specific positions, leading to new structural and electronic outcomes.

## Key findings

- Ni(II) norcorroles react with alkyl radicals at the distal α-position to form nonaromatic bowl-shaped structures.
- Photophysical and electrochemical properties of radical adducts differ from those of the parent Ni(II) norcorrole.
- Density functional theory calculations support the observed radical reactivity patterns.

## Abstract

Norcorrole is a stable 16π-antiaromatic porphyrinoid that exhibits characteristic reactivities and physical properties. Here, we disclose the reaction of Ni(II) norcorroles with alkyl radicals derived from azo radical initiators. The radical selectively attacked the distal α-position relative to the meso-position to construct a nonaromatic bowl-shaped structure. The photophysical and electrochemical properties of the obtained radical adducts were compared to those of the parent Ni(II) norcorrole. The radical reactivity of Ni(II) norcorroles was investigated by density functional theory (DFT) calculations.