Highly Stable Neutral Corrole Radical: Amphoteric Aromatic-Antiaromatic Switching and Efficient Photothermal Conversion.

Abstract

The preparation of novel stable radical systems that survive and may be manipulated under harsh conditions is essential for their practical applications, such as energy storage and conversion materials. Here, we present a facile synthesis of an electrically neutral benzo-fused nickel corrole radical that shows remarkable photo- and thermal stability. The carbon-based organic radical character was confirmed using electron spin resonance and spin population analyses. This radical may be reversibly converted to its aromatic or antiaromatic ion via a one-electron redox process, as indicated by nuclear magnetic resonance chemical shifts and theoretical calculations. Notably, the antiaromatic state is stable, showing intense ring currents with complex pathways. The spectroscopic characteristics and calculated molecular orbitals of the corrole radical exhibit a combination of aromatic and antiaromatic features. On the basis of the aromatic light-harvesting property and antiaromatic emission-free character, the corrole radical exhibits highly robust, efficient photothermal energy conversion in water after encapsulation within nanoparticles, with the unpaired spin simultaneously retained. These results provide a fundamental understanding of the relationship between the (anti)aromaticity and photophysical properties of a porphyrinoid radical and a promising platform for the design of radical-based functional materials.