Abstract: This disclosure provides systems, methods, and apparatus related to nanoparticle/ordered-ligand interlayers. In one aspect, a structure comprises an assembly and a layer of ligands disposed on a surface of the assembly. The assembly comprises a plurality of metal nanoparticles. The metal nanoparticles of the plurality of metal nanoparticles in the assembly are proximate one another. The layer of ligands is operable to detach from the surface of the assembly but to remain proximate the surface of the assembly when the assembly is disposed in an electrolyte and a negative bias is applied to the assembly. An interlayer forms between the assembly and the layer of ligands, with the interlayer comprising desolvated cations from the electrolyte.