Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Multi‐photon absorption (MPA) has attracted interest for applications exploiting the tight spatial control of interaction volume and long wavelength excitation. However, a deficiency of molecules exhibiting higher‐order nPA (<jats:italic>n</jats:italic>‐photon absorption, <jats:italic>n</jats:italic>>2) and a lack of structure–property studies to define the key structural characteristics needed to optimize higher‐order MPA performance have hindered practical development. We herein report the syntheses of second‐ and third‐generation metallodendrimers and assessment of their nonlinear absorption, together with those of zero‐ and first‐generation analogues. We report the first 5PA and 6PA data for an organometallic. The largest dendrimer exhibits exceptional three‐, four‐, five‐ and six‐photon absorption to femtosecond‐pulsed light. The systematically varied compounds highlight the crucial role of metal‐to‐oligo(phenyleneethynylene) charge transfer in promoting outstanding MPA activity.</jats:p>