Coupled Sensitizer–Catalyst Dyads: Electron‐Transfer Reactions in a Perylene–Polyoxometalate Conjugate

Abstract Ultrafast discharge of a single‐electron capacitor: A variety of intramolecular electron‐transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single‐electron events. (et=electron transfer, cr=charge recombination, csr=charge‐shift reaction, PER=perylene, POM=polyoxometalate). magnified image A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long‐lived charge‐transfer state under illumination. They are reduced to a stable π‐radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron‐transfer route by which the charge‐transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through‐space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron‐transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular‐scale capacitors because of efficient electron transfer from the one‐electron‐reduced POM to the excited singlet state of the perylene monoimide.