Similar to the way that atoms bond to form molecules and crystalline structures, colloidal nanocrystals can be combined together to form larger assemblies. The properties of these structures are determined by the properties of individual nanocrystals and by their interactions. The insulating nature of organic ligands typically used in nanocrystal synthesis results in very poor interparticle coupling. We found that various molecular metal chalcogenide complexes can serve as convenient ligands for colloidal nanocrystals and nanowires. These ligands can be converted into semiconducting phases upon gentle heat treatment, generating inorganic nanocrystal solids. The utility of the inorganic ligands is demonstrated for model systems, including highly conductive arrays of gold nanocrystals capped with Sn2S64− ions and field-effect transistors on cadmium selenide nanocrystals.