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Interpenetration is a phenomenon frequently encountered in self-assembled Pd2L4-type coordination cages, while the mechanism of the interpenetration process remains unclear. Here we show the synthesis and solvent-mediated interconversion of highly soluble phenoxazine-based monomeric cage 1 and corresponding interlocked dimer 2. We succeed in the isolation and single-crystal structure analysis of both 1 and 2 with the same guest anion by changing the solvents utilized in self-assembly. The monomeric-to-dimeric cage conversion occurs by heating in weakly coordinating solvents, while dimeric-to-monomeric cage conversion takes place through a disassembly and reassembly process in strongly coordinating solvents at low concentration or by the addition/removal of competing ligand. The interconversion may be driven by the distinct thermodynamic stabilities of 1 and 2 in different solvents. Additionally, Cl– anions template the interpenetration of 1 because of the strong chloride binding affinity of 2 which could serve as an anion-binding catalyst for the C–Cl bond cleavage. While Pd2L4-type coordination cages tend to form interlocked dimers, isolation and characterization of both the cage and its interlocked dimer is very challenging. Herein, the authors report the synthesis and solvent-mediated interconversion of highly soluble phenoxazine-based monomeric cage and corresponding interlocked dimer.
Hong et al. (Thu,) studied this question.