Co-reactant-Free Transformation in Atomically Precise Metal Nanoclusters

Abstract

Transformation chemistry has advanced significantly in recent years as an excellent methodology for synthesizing new nanoclusters and functionalizing the existing ones. However, rational synthesis and fundamental understanding of the structural evolution among clusters have not yet been achieved in nanocluster science. A deeper understanding of the fundamental aspects of structure–property correlation is necessary for the employment of befitting nanoclusters for specific applications. Very recently, the transformation of nanoclusters without the use of conventional co-reactants has been brought to light. These co-reactant-less transformations are triggered by various conditions, such as pH, solvent, light, temperature, etc. In this perspective, we discuss how this unique method of transformation without any co-reactant benefits the basic understanding of growth patterns and the corresponding property evolution in nanoclusters.

Bright near-infrared emission from the Au39(SR)29 nanocluster

“…With the successful development of synthetic methods such as size focusing and transformation, 33–35 molecularly pure, thiolate-protected gold NCs have been achieved. 1 However, the photoluminescence quantum yields (PLQY) of most gold NCs are quite low.…”

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au6(dppp)4]2+ to [Au8(dppp)4Cl2]2+

“…As one of the most important branches of elementary chemical reactions, oxidation plays a pivotal role in the size control of gold nanoclusters. − In addition, with the well-characterized atomic structures of the cluster precursors and products, a variety of oxidation-induced structure and property changes have been elucidated at the molecular level. − So far, the oxidation-induced conversion of gold clusters could be roughly classified into three types. The first one corresponds to the structure-maintained oxidation, wherein the precursor is mainly differentiated from the product on the charge state {e.g., [Au 25 (SR) 18 ] − → [Au 25 (SR) 18 ] 0 → [Au 25 (SR) 18 ] + , − [Au 25 (SePh) 5 (PPh 3 ) 10 Cl 2 ] + → [Au 25 (SePh) 5 (PPh 3 ) 10 Cl 2 ] 2+ , and [Au 133 (SR) 52 ] 0 → [Au 133 (SR) 52 ] + } .…”

A Comprehensive Analysis of Luminescent Crystallized Cu Nanoclusters

“…Beyond the synthesis of NCs, ensuring their stability is of paramount significance. − Cu, despite sharing the same group on the periodic table with Au and Ag, exhibits a notably distinct half-cell reduction potential. This differential potential significantly influences the stability and the associated properties of the newly synthesized NCs. − Furthermore, the structural architecture of ligands, molecules, or ions that attach to the surface of the NCs assumes a pivotal role in shaping the overall stability of these NCs. , Ligands act as a protective shield, forming a crucial layer that separates the metallic core of the NC from the external environment. , This barrier contributes significantly to the structural integrity of the NC. , Interestingly, in the traditional noble metal NCs, it has been observed that the size and conformation of these protective ligands also influence the precise properties of the NCs.…”

“…Beyond the synthesis of NCs, ensuring their stability is of paramount significance. 23 − 25 Cu, despite sharing the same group on the periodic table with Au and Ag, exhibits a notably distinct half-cell reduction potential. This differential potential significantly influences the stability and the associated properties of the newly synthesized NCs.…”