Since the discovery of metal chalcogenide complexes (MCCs) as capping ligands for colloidal nanocrystals (NCs) in 2009, the chemistry of inorganic ligands for NCs has provided a new paradigm for surface design of nanomaterials. Various inorganic anions including MCCs, metal-free chalcogenides, oxoanions/oxometallates, and halides/pseudohalides/halometallates have been employed to replace the original long-chain organic ligands on NCs. This ligand exchange can also be achieved through a two-step route using ligands stripping agents like HBF4. This review outlines recent advances in inorganically-capped colloidal NCs and details the ligand exchange process for NCs using MCCs and metal-free chalcogenides. The binding affinities of ligands to NC surface have been rationalized in terms of Pearson's hard and soft acids and bases (HSAB) principle. We also demonstrate that inorganic ligands broaden the functionality of NCs by tailoring their electro-optical properties or generating new inorganic phases through chemical reactions between nanomaterials and their surface ligands. Especially promising are the electronic, optoelectronic, and thermoelectric applications of solution-processed, inorganically-capped colloidal NCs, which substantially outperform their organically-capped couterparts.
©2014 Walter de Gruyter Berlin/Boston