Phosphorescent hexamolybdenum cluster complexes with pyrene and anthracene carboxylates exhibit energy transfer from the grafted ligands to the {Mo6I8} core. The complex with the pyrene ligands exhibits the highest brightness of emission ever reported for a Mo6 cluster complex excited in the near‐UV region (ϵ355 = 2.3 105 M–1 cm–1, ΦL = 0.60). These antenna systems possess attractive features as UV/Red light convertors, optical oxygen sensors, or sensitizers of singlet oxygen.

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