In a mixed-valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter-cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed-valence polyoxometalates were electrically wired by cationic π-molecules of tetrathiafulvalene substituted with pyridinium. Electron-transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π-molecules.

In a mixed‐valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter‐cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed‐valence polyoxometalates were electrically wired by cationic π‐molecules of tetrathiafulvalene substituted with pyridinium. Electron‐transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π‐molecules.

In a mixed‐valence polyoxometalate electrons are usually delocalized within the cluster anion because of the low intercluster interaction. In their Communication on R. Tsunashima et al. show how mixed‐valence polyoxometalate clusters can be electrically wired together by cationic π‐molecules of tetrathiafulvalene derivatives. The electron‐transport characteristics of the single crystal arise from electron hopping through the strong interactions between the clusters and cationic π‐molecules.

Elektronen in gemischtvalenten Polyoxometallaten …︁ …︁ sind normalerweise wegen der schwachen Wechselwirkungen zwischen den Clustern über ein Clusteranion delokalisiert. In ihrer Zuschrift auf zeigen R. Tsunashima et al., wie gemischtvalente Polyoxometallatcluster durch Tetrathiafulvalen‐Derivate elektrisch verbunden werden können. Der Elektronentransport im Einkristall beruht auf einem Elektronenhüpfen infolge der starken Wechselwirkungen zwischen den Clustern und den kationischen π‐Molekülen.