Stimuli-responsive materials have attracted considerable attention due to their ability to react to external triggers. Plasmonic nanohybrids incorporating both gold nanoparticles and stimuli-responsive materials can enable the active control of plasmonic properties such as plasmon resonance energy and charge transfer through soft interfaces in the nanohybrids. However, the broad application of plasmonic nanohybrids requires a deep understanding of the underlying mechanisms that govern their active control and responsiveness. In this work, we examine how the arrangement of gold nanocubes (AuNCs) within a poly(N-isopropylacrylamide) (PNIPAM) matrix, together with the polymer’s structural organization, collectively governs the localized surface plasmon resonance (LSPR) response in single hybrid nanostructures. To achieve this, single-particle dark-field hyperspectral imaging was used to monitor the plasmonic characteristics of the nanohybrids at a subpopulation level. Through these measurements, we revealed asymmetric plasmon line shapes based on the relative location of the AuNC in the nanohybrid, highlighting the importance of morphological arrangement for plasmonic tuning. Furthermore, our single-particle approach uncovered internal heterogeneity of the plasmonic nanohybrids, which shows great promise in the understanding of structural-spectral relationships that traditional ensemble techniques are unable to discern. In addition, conformational heterogeneity in the polymer domain can be systemically characterized via gap surface plasmon analyzed in a particle on a mirror system. In conclusion, this work provides an insight into how the influence of the plasmonic core on polymer dynamics, thereby enabling the rational design of flexible and easily processable devices and architectures.
