Supramolecular polynuclear clusters sustained cubic hydrogen bonded frameworks with octahedral cages for reversible photochromism.
basic_science · Level V
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- Record sourced from PubMed, PMID 38555300.
- Also identified by DOI 10.1038/s41467-024-47058-1 and PMC identifier 10981757.
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Abstract
Developing supramolecular porous crystalline frameworks with tailor-made architectures from advanced secondary building units (SBUs) remains a pivotal challenge in reticular chemistry. Particularly for hydrogen-bonded organic frameworks (HOFs), construction of geometrical cavities through secondary units has been rarely achieved. Herein, a body-centered cubic HOF (TCA_NH<sub>4</sub>) with octahedral cages was constructed by a C<sub>3</sub>-symmetric building block and NH<sub>4</sub><sup>+</sup> node-assembled cluster (NH<sub>4</sub>)<sub>4</sub>(COOH)<sub>8</sub>(H<sub>2</sub>O)<sub>2</sub> that served as supramolecular secondary building units (SSBUs), akin to the polynuclear SBUs in reticular chemistry. Specifically, the octahedral cages could encapsulate four homogenous haloforms including CHCl<sub>3</sub>, CHBr<sub>3</sub>, and CHI<sub>3</sub> with truncated octahedron configuration. Crystallographic evidence revealed the cages served as spatially-confined nanoreactors, enabling fast, broadband photochromic effect associated with the reversible photo/thermal transformation between encapsulated CHI<sub>3</sub> and I<sub>2</sub>. Overall, this work provides a strategy by shaping SSBUs to expand the framework topology of HOFs and a prototype of hydrogen-bonded nanoreactors to accommodate reversible photochromic reactions.