Polyoxometalate-Based Metal–Organic Frameworks for Selective Oxidation of Aryl Alkenes to Aldehydes

Polyoxometalates (POMs) show considerable catalytic performance toward the selective oxidation of alkenes to aldehydes, which is commercially valuable for the production of pharmaceuticals, dyes, perfumes, and fine chemicals. However, the low specific surface area of POMs as heterogeneous catalysts and poor recyclability as homogeneous catalysts have hindered their wide application. Dispersing POMs into metal–organic frameworks (MOFs) for the construction of POM-based MOFs (POMOFs) suggests a promising strategy to realize the homogeneity of heterogeneous catalysis. Herein, we report two new POMOFs with chemical formulas of [Co­(BBTZ)<sub>2</sub>]­[H<sub>3</sub>BW<sub>12</sub>O<sub>40</sub>]·10H<sub>2</sub>O (<b>1</b>) and [Co<sub>3</sub>(H<sub>2</sub>O)<sub>6</sub>(BBTZ)<sub>4</sub>]­[BW<sub>12</sub>O<sub>40</sub>]·NO<sub>3</sub>·4H<sub>2</sub>O (<b>2</b>) (BBTZ = 1,4-bis­(1,2,4-triazol-1-ylmethyl)­benzene) for the selective oxidation of alkenes to aldehydes. Compound <b>1</b> possesses a non-interpenetrated three-dimensional (3D) <i>cds</i>-type open framework with a 3D channel system. Compound <b>2</b> displays a 3D polyrotaxane framework with one-dimensional channels along the [100] direction. In the selective oxidation of styrene into benzaldehyde, compound <b>1</b> can achieve a 100% conversion in 4 h with 96% selectivity toward benzaldehyde, which is superior to that of compound <b>2</b>. A series of control experiments reveal that the co-role of [BW<sub>12</sub>O<sub>40</sub>]<sup>5–</sup> and Co<sup>2+</sup> active center as well as a more open framework feature co-promote the catalytic property of the POMOFs in this case. This work may suggest a new option for the development of POMOF catalysts in the selective oxidation of alkenes.