Steric Hindrance Favors σ Dimerization over π Dimerization for Julolidine Dicyanomethyl Radicals

Metastable radicals exist in a steady-state equilibrium in solution with dimers, which can be either σ dimers or π dimers. Here, we show that steric hindrance at the para position causes julolidine-derived dicyanomethyl radicals to form σ dimers rather than π dimers, the opposite behavior as seen in other carbon-centered radicals, where steric hindrance typically favors pimerization. The change in dimerization mode can be attributed to weaker London dispersion forces and a decreased orbital overlap in the sterically hindered dicyanomethyl radical π dimers, while the bulky groups exert relatively little effect on the energy of the σ dimer.