Enhancing Interfacial Charge Transport in Gold Nanoparticle@Polyaniline Hybrids via $N$‐Heterocyclic Carbene Linkers

N-Heterocyclic carbenes (NHCs) have emerged as a unique class of ligands for gold nanoparticles (Au NPs), combining strong metal binding with intrinsic electronic conductivity. Yet over the past decade, studies on Au NP@NHC systems have primarily focused on their stability, while the conductivity of NHCs has remained largely unexplored due to synthesis challenges. Here, we present a synthetic strategy that addresses this gap by employing amino-functionalized NHC-Au complexes with in situ oxidative polymerization of polyaniline (PANI) to yield electronically coupled Au NP@NHC-PANI hybrids in aqueous media. This strategy enables both a controlled PANI shell growth and introduction of an electronically active NHC interlayer. Single-particle scattering spectroscopy reveals that NHCs improve the interfacial electronic coupling as evidenced by pronounced plasmonic linewidth broadening. Conductivity measurements further confirm that NHCs enhance charge transport: conductive atomic force microscopy (C-AFM) shows an increase in contact current from 14.6 to 99.4 pA under a 300-mV bias, while lateral four-probe conductance increases from 0.17 to 3.5 nS. ... mehrThese results provide the first direct experimental evidence of the conductive role of NHCs in hybrid NP-polymer systems, establishing a new interface-engineering strategy for the rational design of electronically delocalized nanostructures and their applications in nanoelectronics.