Journal
FRONTIERS IN CHEMISTRY
Volume 6, Issue -, Pages -Publisher
FRONTIERS MEDIA SA
DOI: 10.3389/fchem.2018.00330
Keywords
ligand effect; nanoparticle atomic structure; metal ligand interface; ligand-ligand interaction; nanoparticle synthesis
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Funding
- NSF [1539035]
- CINECA Supercomputing Centre within the ISCRA Programme
- [NSF-CHE-1255519]
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The nature of the ligands dictates the composition, molecular formulae, atomic structure and the physical properties of thiolate protected gold nanomolecules, Au-n(SR)(m). In this review, we describe the ligand effect for three classes of thiols namely, aliphatic, AL or aliphatic-like, aromatic, AR, or bulky, BU thiol ligands. The ligand effect is demonstrated using three experimental setups namely: (1) The nanomolecule series obtained by direct synthesis using AL, AR, and BU ligands; (2) Molecular conversion and interconversion between Au-38(S-AL)(24), Au-36(S-AR)(24), and Au-30(S-BU)(18) nanomolecules; and (3) Synthesis of Au-38, Au-36, and Au-30 nanomolecules from one precursor Au-n(S-glutathione)(m) upon reacting with AL, AR, and BU ligands. These nanomolecules possess unique geometric core structure, metal-ligand staple interface, optical and electrochemical properties. The results unequivocally demonstrate that the ligand structure determines the nanomolecules' atomic structure, metal-ligand interface and properties. The direct synthesis approach reveals that AL, AR, and BU ligands form nanomolecules with unique atomic structure and composition. Similarly, the nature of the ligand plays a pivotal role and has a significant impact on the passivated systems such as metal nanoparticles, quantum dots, magnetic nanoparticles and self-assembled monolayers (SAMs). Computational analysis demonstrates and predicts the thermodynamic stability of gold nanomolecules and the importance of ligand-ligand interactions that clearly stands out as a determining factor, especially for species with AL ligands such as Au-38(S-AL)(24).
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