Coordination Assembly of Discoid Nanoparticles

Abstract

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS2 pyrite nanoparticles (NPs) that can facilitate charge transport. Zn2+ ions form supramolecular complexes with carboxylate end‐groups on NP surface, leading to multiparticle sheets with liquid‐crystal‐like organization. Conductivity and Hall carrier mobility of the p‐type layered semiconductor films with Zn2+ coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self‐organized materials combining nanoscale and supramolecular structural motifs.Zinc ions are the “glue”: FeS2 nanoparticles (NPs) spontaneously assemble into sheets because of coordination bridging between Zn2+ and carboxylate groups on the NP surface. Conductivity and Hall carrier mobility of the p‐type semiconductor films exceed those known for coordination compounds and MOFs. The nanoscale porosity and fast hole transport of assembled sheets leads to high electrocatalytic activity of the NP films.