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Coordination-bond-directed synthesis of hydrogen-bonded organic frameworks from metal–organic frameworks as templates† † Electronic supplementary information (ESI) available. CCDC 2082445–2082447. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d1sc03962h

ABSTRACT: Controlled synthesis of hydrogen-bonded organic frameworks (HOFs) remains challenging, because the self-assembly of ligands is not only directed by weak hydrogen bonds, but also affected by other competing van der Waals forces. Herein, we demonstrate the coordination-bond-directed synthesis of HOFs using a preformed metal–organic framework (MOF) as the template. A MOF (CuI-TTFTB) based on two-coordinated CuI centers and tetrathiafulvalene-tetrabenzoate (TTFTB) ligands was initially synthesized. CuI-TTFTB was subsequently oxidized to the intermediate (CuII-TTFTB) and hydrated to the HOF product (TTFTB-HOF). Single-crystal-to-single-crystal (SC-SC) transformation was realized throughout the MOF-to-HOF transformation so that the evolution of structures was directly observed by single-crystal X-ray diffraction. The oxidation and hydration of the CuI center are critical to breaking the Cu–carboxylate bonds, while the synergic corbelled S⋯S and π⋯π interactions in the framework ensured stability of materials during post-synthetic modification. This work not only provided a strategy to guide the design and discovery of new HOFs, but also linked the research of MOFs and HOFs. The MOF-to-HOF transformation was realized in a single-crystal-to-single-crystal manner by the oxidation and hydration of the CuI center in CuI-TTFTB. The corbelled S⋯S and π⋯π interactions ensured the framework stability during transformation.

SUBMITTER: Su J

PROVIDER: S-EPMC8565389 | biostudies-literature |

REPOSITORIES: biostudies-literature

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