Supramolecular Aggregation Control in Polyoxometalates Covalently Functionalized with Oligoaromatic Groups

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‐P2W17O61]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. The synthesis of Dawson type molecular metal oxides covalently functionalized with oligoaromatic groups is reported using a facile CLICK chemistry approach. The supramolecular chemistry of these organic‐inorganic hybrids as well as their interactions with model photosensitizers are studied as basis for photoinduced electron transfer and storage systems.