Stable Olympicenyl Radicals and Their π‑Dimers

An olympicenyl radical, a spin 1/2 hydrocarbon radical with C 2v symmetry and uneven spin distribution, remains elusive despite the considerable theoretical research interest. Herein, we report syntheses of two air-stable olympicenyl radical derivatives, OR1 and OR2, with half-life times (τ1/2) in air-saturated solution of 7 days and 34 days. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. X-ray crystallographic analysis revealed unique 20-center–2-electron head-to-tail π-dimer structures with intermolecular distances shorter than the sum of van der Waals radius of carbon. The ground state of the π-dimers was found to be singlet, with singlet–triplet energy gaps estimated to be −2.34 kcal/mol and −3.28 kcal/mol for OR1 and OR2, respectively, by variable-temperature electron spin resonance (ESR) spectroscopy. The monomeric radical species were in equilibrium with the π-dimer in solution, and the optical and electrochemical properties of the monomers and π-dimers in solution were investigated by UV–vis–NIR spectroscopy and cyclic voltammetry, revealing a concentration-dependent nature. Theoretical calculations illustrated that upon formation of a π-dimer the local aromaticity of each monomer was enhanced, and spatial ring current between the monomers was present, which resulted in an increment of aromaticity of the interior of the π-dimer.