CLICK-chemistry has become a universal route to covalently link organic molecules functionalized with azides and alkynes, respectively. Here, we report how CLICK-chemistry can be used to attach oligoaromatic organic moieties to Dawson-type polyoxometalates. In step one, the lacunary Dawson anion [α2 -P2 W17 O61 ]6- is functionalized with phosphonate anchors featuring peripheral azide groups. In step two, this organic-inorganic hybrid undergoes microwave-assisted CLICK coupling. We demonstrate the versatility of this route to access a series of Dawson anions covalently functionalized with oligoaromatic groups. The supramolecular chemistry and aggregation of these systems in solution is explored, and we report distinct changes in charge-transfer behavior depending on the size of the oligoaromatic π-system.
Keywords: organic-inorganic hybrid; organofunctionalization; photosensitizer; polyoxometalate; supramolecular.
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.