Controlling Intramolecular and Intermolecular Electronic Coupling of Radical Ligands in a Series of Cobaltoviologen Complexes

Abstract

Controlling electronic coupling between multiple redox sites is of interest for tuning the electronic properties of molecules and materials. While classic mixed-valence (MV) systems are highly tunable, e.g., via the organic bridges connecting the redox sites, metal-bridged MV systems are difficult to control because the electronics of the metal cannot usually be altered independently of redox-active moieties embedded in its ligands. Herein, this limitation was overcome by varying the donor strengths of ancillary ligands in a series of cobalt complexes without directly perturbing the electronics of viologen-like redox sites bridged by the cobalt ions. The cobaltoviologens [1_X-Co]ⁿ⁺ feature four 4-X-pyridyl donor groups (X = CO₂Me, Cl, H, Me, OMe, NMe₂) that provide gradual electronic tuning of the bridging Co^II centers, while a related complex [2-Co]ⁿ⁺ with NHC donors supports exclusively Co^III states even upon reduction of the viologen units. Electrochemistry and IVCT band analysis indicate that the MV states of these complexes have electronic structures ranging from fully localized ([2-Co]⁴⁺; Robin-Day Class I) to fully delocalized ([1_CO2Me-Co]³⁺; Class III) descriptions, demonstrating unprecedented control over electronic coupling without changing the identity of the redox sites or bridging metal. Additionally, single-crystal XRD characterization of the homovalent complexes [1_H-Co]²⁺ and [1_H-Zn]²⁺ revealed radical-pairing interactions between the viologen ligands of adjacent complexes, representing a type of through-space electronic coupling commonly observed for organic viologen radicals but never before seen in metalloviologens. The extended solid-state packing of these complexes produces 3D networks of radical π-stacking interactions that impart unexpected mechanical flexibility to these crystals.