Metal-organic frameworks (MOFs) are undergoing an intensive investigation in the field of heterogeneous catalysis. This is attributed to their high surface area, well-defined coordination nano-space, diversity in metal and functional groups, as well as the ability to retain crystallinity and regularity after catalytic reactions. MOFs containing mixed valence state ions are emerging microporous materials, which have unique properties as well as significant potential applications. The CuI-catalyzed azide-alkyne cycloaddition (CuAAC) is arguably the most powerful toolbox for polymer functionalization and coupling applications in modern polymer chemistry. Conventional catalysts suffer from their inefficient catalytic ability due to low solubility and low stability under the reaction conditions. Some improved liganded CuI systems are able to significantly increase the solubility of CuI in both organic and aqueous solvents and hence present enhanced catalytic abilities. However, the dissolved CuI ions might result in potential contaminations, which in turn lead to complicated purification steps. In this study, we reported a study on the catalytic properties of a reduced Cu-MOF (rCu-MOF). As far as we know, this is the first example of reduced MOF nanoparticles (containing CuI ions) which can facilitate CuAAC click chemistry. The rCu-MOF was synthesized in the laboratory (Fig. 1a) and well-characterized. The catalytic ability of the rCu-MOFs was then demonstrated by a series of successfully polymer functionalizationand coupling reactions (Fig. 1b and 1c). This rCu-MOF catalyst also presents advantages, such as high hydrothermal stability and facile recyclability in comparison with conventional catalysts. Compared with the conventional copper halide catalyst, higher activity and facile recyclability of the rCu-MOF catalyst was observed. These properties combined with its ease of synthesis, lack of heavy metal contamination and high structural stability make the rCu-MOFs attractive catalytic materials for potential industrial applications.

Reduced copper metal-organic frameworks: A heterogeneous catalyst for click chemistry

253rd National Meeting (2017)

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