A Redox-active Phenothiazine-based Pd2L4-type Coordination Cage and Its Isolable Crystalline Polyradical Cations.

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14•+ through post-synthetic oxidation of a redox-active phenothiazine-based Pd2L4-type coordination cage 1. It's worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5-di-tert-butyl-4-methoxyphenyl substituent. The generation of 14•+ through reversible electrochemical oxidation is investigated by in situ UV-vis-NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14•+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X-ray diffraction analysis of 14•+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14•+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages.

Self-assembly of conformation-adaptive dihydrophenazine-based coordination cages.

In this study, we designed and synthesized three conformation-adaptive Pd2L4- and Pd3L6-type coordination cages based on three dihydrophenazine-based ligands with different lengths. Interestingly, the shorter ligands L1 and L2 self-assembled into Pd2L4-type coordination cages while the longer ligand L3 formed Pd3L6-type one, mainly driven by the anion template effect. All coordination cages were confirmed through single-crystal X-ray diffraction, and their structural conformations underwent great changes compared with those of their corresponding ligands. Moreover, the conformational changes also significantly affected their photophysical and electrochemical properties which were distinct from their parent ligands.