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Some free radicals are stable enough to be isolated, but most are either unstable transient species or exist as metastable species in equilibrium with a dimeric form, usually a spin-paired sigma dimer or a pi dimer (pimer). To gain insight into the different modes of dimerization, we synthesized and evaluated a library of 15 aryl dicyanomethyl radicals in order to probe what structural and molecular parameters lead to σ- versus π-dimerization. We evaluated the divergent dimerization behavior by measuring the strength of each radical association by variable-temperature electron paramagnetic resonance spectroscopy, determining the mode of dimerization (σ- or π-dimer) by UV–vis spectroscopy and X-ray crystallography, and performing computational analysis. We evaluated three different hypotheses to explain the difference in the dimerization behavior: (1) that the dimerization behavior is dictated by radical spin densities; (2) that it is dictated by radical polarizability; (3) that it is dictated by London dispersion stabilization of the pimer. However, no single parameter model in itself was predictive. Two-parameter models incorporating either the computed degree of spin delocalization or the radical polarizability as well as computed estimates for the attractive London dispersion forces in the π-dimers lead to improved forecasts of σ- vs π-dimerization mode, and suggest that a balance of spin delocalization of the isolated radical as well as attractive forces between the stacked radicals, govern the formation of diradical pimers.
Available at: http://works.bepress.com/arthur_winter/32/
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/jacs.0c00190. Posted with permission.