| Abstract: | Herein, we demonstrate that the dimerization behavior of amine‐substituted dicyanomethyl radicals can be switched from σ‐ to π‐dimerization simply by varying the electron‐donating substituents. For dicyanomethyl radicals with a 4,4′‐ditolylamine ( DT. ) or a phenothiazine ( PT. ) substituent, the monomeric radical form and the corresponding dimer connected by a reversible C?C bond (σ‐dimer) are in equilibrium in solution. On the other hand, the radical with the julolidine skeleton ( JD. ) does not undergo σ‐dimerization and was isolated as a stable radical in spite of the absence of bulky protecting groups. X‐ray single‐crystal analysis revealed that JD. forms the π‐dimer in the crystalline state, and variable‐temperature spectroscopy showed that JD. is in equilibrium with the π‐dimer in toluene solution. DFT calculations point to the importance of electrostatic interactions as a driving force for the π‐dimerization of JD. because of its polarized structure. |
