A little spin on the side: solvent and temperature dependent paramagnetism in [RuII(bpy)2(phendione)]2+

Abstract

Solvent and temperature dependent paramagnetism is reported for the complex [Ru^II(bpy)₂(phendione)](PF₆)₂ (bpy = 2,2′-bipyridine, phendione = 1,10-phenanthroline-5,6-dione), 1. Magnetometry, ¹H-NMR, EPR and substituent effects confirm that the paramagnetic character is localized on the phendione ligand, and arises due to mixing of the MLCT excited state with an open shell triplet state on the phendione moiety, a process that is most likely driven by aromatization. The stabilized open shell phendione structure, in which the triplet lies lower in energy than the singlet, can then be thermally populated from the ground state of the complex. This process is facilitated by admixture of singlet character from the MLCT state. Paramagnetic behavior is absent in the free phendione ligand, and disappears in the presence of Lewis acids and in the presence of water due to hydrogen bonding (or hydrate formation at sufficient water concentrations). Control experiments rule out the presence of monoradicals such as semiquinone anions. Implications for spin filtering, sensing, and other electronic applications using such structures are discussed.