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  • Controlling intramolecular and intermolecular electronic coupling of radical ligands in a series of cobaltoviologen complexes
Title: Controlling intramolecular and intermolecular electronic coupling of radical ligands in a series of cobaltoviologen complexes

Controlling electronic coupling between two or more 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 modular 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, we overcome this limitation 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 [1X-Co]n+ feature four 4-X-pyridyl donor groups (X = CO2Me, Cl, H, Me, OMe, NMe2) that provide gradual tuning of the electronics of the bridging CoII centers, while a related complex [2-Co]n+ with NHC donors supports exclusively CoIII states even upon reduction of the viologen ligands. Electrochemistry and IVCT band analysis reveal that the MV states of these complexes have electronic structures ranging from fully localized ([2-Co]4+; Robin-Day Class I) to fully delocalized ([1CO2Me-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 [1H-Co]2+ and [1H-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.

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Award ID(s):
2117792
PAR ID:
10529801
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
ChemRxiv
Date Published:
Format(s):
Medium: X
Institution:
Rutgers University
Sponsoring Org:
National Science Foundation
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