Seeded‐Growth of PCN‐224 onto Plasmonic Nanoparticles: Photoactive Microporous Nanocarriers

This study addresses the fabrication of microporous plasmonic nanocomposites (NCs) by using plasmonic nanoparticles (i.e., gold bipyramids, AuB) as seeds to grow microporous shells, specifically, metal–organic frameworks (MOF) PCN‐224 of increasing thickness from 69 to 138 nm. This method is based on using a previously synthesized Zr₆‐oxo cluster and unfolds at room temperature. Notably, it is demonstrated that the concentration of the AuB seeds determines both the yield of NCs and the resultant thickness of the PCN‐224 shell, illustrating the seeded growth mechanism. Furthermore, it is found that the thermoplasmonic response of the NCs is dominated by the thickness of the microporous shell, with thicker shells having enhanced thermal confinement properties than thinner ones. As a proof of concept, the NCs are loaded with cresyl violet (CV), a lysosomal fluorescent marker. This serves to demonstrate the thermoplasmonic‐induced intracellular release of CV by the photostimulation of the AuB's plasmonic near‐infrared (NIR) band. Moreover, the NCs display exceptional efficacy as photodynamic agents when photostimulated at the PCN‐224's Soret band. In summary, this study offers a facile, efficient, and reproducible methodology for the fabrication of NCs with a controlled geometry while unlocking new possibilities in the field of nanoMOFs as multifunctional theranostic probes.