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The complexation of plasmonic nanoparticles (NPs) and thermoresponsive microgels is widely exploited for applications, but a microscopic description of the mechanisms governing the spatial organization of the NPs is still lacking. Combining small angle X-ray scattering, state-of-the-art simulations and a simple toy model, we uncover how the volume phase transition of microgels controls NP-NP interactions, establishing for the first time a microscopic link between plasmon coupling and NP local structure. Our study paves the way to experimentally investigate phase transitions on controlled curved surfaces at the nanoscale.

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