Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd<sub>2</sub>L<sub>4</sub> and Pd<sub>4</sub>L<sub>8</sub> coordination cages.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 40082455.
- Also identified by DOI 10.1038/s41467-025-57876-6 and PMC identifier 11906823.
- Licence recorded as CC BY-NC-ND.
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Abstract
Interpenetration is a phenomenon frequently encountered in self-assembled Pd<sub>2</sub>L<sub>4</sub>-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<sup>-</sup> 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.