Nano Gold: From Nanoparticles to Atomically Precise Nanoclusters †

Huili Wang; Jean-Luc Pozzo; Didier Astruc

Abstract

Gold nanoparticles (AuNPs), with size between 3 and 100 nm are well-known for their optical properties due to their plasmon band related to the resonance of the collective oscillation of their surface electron cloud matching the incident light wavelength. When the AuNPs are smaller than 2.3 nm, they are no longer plasmonic with fcc structures, but they fall in a quantum size regime of ultra-small AuNPs with specific structural, electronic, optical and catalytic properties resulting from molecular diagrams. They are atomically precise nanoclusters (APNCs), and their construction usually follows the Mackay maximum compacity with successive concentric shells of (10i² + 2) atoms, meaning that for i = 1, the central Au atom is surrounded by 12 Au atoms Au@Au₁₂ in many icosahedral Au₁₃ clusters and the second layer (i = 1) contains 42 atoms with Au@Au₁₂@Au₄₂ in a Au₅₅ cluster (Schmid’s cluster), etc. The icosahedron is the most frequently observed structure in Au APNCs, but the tetra-, hexa-, deca, icosa- and cubocta-hedron structures are also found, and all these symmetrical structures contribute to the cluster stability, as well as the surface Au-S staples. Since each Au atom contributes its single 6s electron to the non-bonding cluster valence electrons, an exceptional stability is obtained when the total number of non-bonding valence electrons contributing to the clusterification reaches one of the magic numbers 2, 8, 18, 34, 58, 92, 138, … corresponding to closed electron shells, when the compacity is high (quasi-spherical). For instance, the 2-electron Au₃⁺ and 8-electron Au₁₃⁵⁺ cores are named superatom clusters. Many clusters, however, also deviate from this trend. The most common cluster series [Au₂₅(SR)₁₈]⁻ composed of the 8-electron Au₁₃⁵⁺ core and 6[Au(I)₂(SR)₆]²⁻ staples are superatom clusters. Although the size-focusing synthesis of the major groups of APNCs is that of thiolate clusters, whose accurate synthesis was astutely focused by the Jin group, the first 8-electron icosahedral phosphine Au₁₃ cluster was predicted 50 years ago, then synthesized by the Mingos group in 1981, and in the 2010s new series of Au APNCs appeared with the alkynyl and carbene [both Bertrand-type and N-Heterocyclic Carbene (NHC)-type]) Au APNCs. All these APNC families present very promising electronic, photophysical and catalytic, (including electrocatalytic and photocatalytic) properties that are now exploited by researchers toward biomedicine and energy conversion processes, as well as those of small AuNPs whose catalytic properties were pioneered by Haruta.

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