Metal–Ligand Interactions and Their Roles in Controlling Nanoparticle Formation and Functions

Conspectus Functional nanoparticles (NPs) have been studied extensively in the past decades for their unique nanoscale properties and their promising applications in advanced nanosciences and nanotechnologies. One critical component of studying these NPs is to prepare monodisperse NPs so that their physical and chemical properties can be tuned and optimized. Solution phase reactions have provided the most reliable processes for fabricating such monodisperse NPs in which metal–ligand interactions play essential roles in the synthetic controls. These interactions are also key to stabilizing the preformed NPs for them to show the desired electronic, magnetic, photonic, and catalytic properties. In this Account, we summarize some representative organic bipolar ligands that have recently been explored to control NP formation and NP functions. These include aliphatic acids, alkylphosphonic acids, alkylamines, alkylphosphines, and alkylthiols. This ligand group covers metal–ligand interactions via covalent, coordination, and electrostatic bonds that are most commonly employed to control NP sizes, compositions, shapes, and properties. The metal–ligand bonding effects on NP nucleation rate and growth can now be more thoroughly investigated by in situ spectroscopic and theoretical studies. In general, to obtain the desired NP size and monodispersity requires rational control of the metal/ligand ratios, concentrations, and reaction temperatures in the synthetic solutions. In addition, for multicomponent NPs, the binding strength of ligands to various metal surfaces needs to be considered in order to prepare these NPs with predesigned compositions. The selective ligand binding onto certain facets of NPs is also key to anisotropic growth of NPs, as demonstrated in the synthesis of one-dimensional nanorods and nanowires. The effects of metal–ligand interactions on NP functions are discussed in two aspects, electrochemical catalysis for CO 2 reduction and electronic transport across NP assemblies. We first highlight recent advances in using surface ligands to promote the electrochemical reduction of CO 2 . Several mechanisms are discussed, including the modification of the catalyst surface environment, electron transfer through the metal–organic interface, and stabilization of the CO 2 reduction intermediates, all of which facilitate selective CO 2 reduction. These strategies lead to better understanding of molecular level control of catalysis for further catalyst optimization. Metal–ligand interaction in magnetic NPs can also be used to control tunneling magnetoresistance properties across NPs in NP assemblies by tuning NP interparticle spacing and surface spin polarization. In all, metal–ligand interactions have yielded particularly promising directions for tuning CO 2 reduction selectivity and for optimizing nanoelectronics, and the concepts can certainly be extended to rationalize NP engineering at atomic/molecular precision for the fabrication of sensitive functional devices that will be critical for many nanotechnological applications.