Diradical Silver Derivative of Nitronyl Nitroxide: Synthesis, Structure, and Conformation-Dependent Magnetic Properties

Nitronyl nitroxides (NNs) are widely employed in chemistry, physics, and materials science due to their inherently high stability and magnetic properties. However, the synthesis of C(2)-organoelement derivatives remains a challenging task. This paper reports on the efficient synthesis and characterization of an unusual organosilver complex consisting of the [Ag–(IPr)2]+ cation and the [Ag–(NN)2]− anion. The salt [Ag–(IPr)2][Ag–(NN)2] was prepared in high yields (88–96%) by two synthetic routes: by reacting the carbene ligand precursor IPr·HCl with Ag2O and nitronyl nitroxide NN–H, or by addition of NN–H/tBuONa to a THF solution of IPrAgCl (generated in situ from IPr·HCl and Ag2O) under microwave irradiation. Electrochemical analysis of [Ag–(IPr)2][Ag–(NN)2] revealed a reversible one-electron oxidation peak at E1/2 = −0.258 V and an irreversible reduction peak at Ep = −2.169 V, which is likely related to the electrochemical transformation of the nitronyl nitroxide moieties. Crystallization from an acetone/benzene solution yielded crystals of [Ag–(IPr)2][Ag–(NN)2]·2H2O solvate, in which the diradical anion [Ag–(NN)2]− is bound to two water molecules by hydrogen bonds. These hydrogen bonds stabilize a planar conformation of the [Ag–(NN)2]− anion, in which both NN fragments lie in the same plane and, according to DFT calculations, are linked by fairly strong antiferromagnetic interaction. DFT calculations also predict the dissociation of the complex with water in toluene solution and a conformational change leading to the appearance of about 90° between NN fragments and a significant decrease in exchange interaction.