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.
Molecular level understanding of the structural growth patterns and property evolution in nanoclusters (NCs) is crucial for the design and rational synthesis of clusters for specific properties and applications. In this regard, transformation has always been a versatile approach to achieve atomic precision with atomic purity and a deeper understanding of the growth mechanisms of noble metal NCs. To the latter end, we have demonstrated a structural transformation of Au 44 (SPh-t Bu) 28 to Au 36 (SPh-t Bu) 24 NC, which occurred through the deassembly of an Au 8 (SPh-t Bu) 4 fragment. Kinetic studies conducted on the transformation showed that it follows zero-order kinetics with a low activation energy pathway. Theoretical studies demonstrated that this process happens via surface restructuring of the core-ligand interface, which was found to be the rate-determining step of this transformation. Based on this, a plausible mechanistic pathway for the transformation have been proposed which we envision, will provide useful insights into NC structure evolution.L igand-protected gold nanoclusters have attracted significant interest in the past few decades as promising materials for fundamental research as well as for applications in various fields such as sensing, optoelectronics, catalysis, and biomedical applications. 1−7 Even though nanoclusters (NCs) provide the advantage of atomically precise synthesis and complete structure elucidation using X-ray crystallography, 8−17 rational synthesis of a NC with the desired size, structure, or properties is yet to be achieved. Herein lies the importance of understanding the structural growth patterns as well as corresponding property evolutions from existing NCs rather than increasing the library of these noble metal NCs. To gain a deeper understanding of the structural growth as well as the corresponding property evolution in NCs, it is desirable to study NCs with similar structures and periodicities in their properties. Recently, a few NC-series have been discovered in the family of thiolate-protected gold NCs, which show periodicity in their structure and properties. 18−25 Such periodicities are unique since the ultrasmall size of NCs gives rise to the quantum confinement effect, which causes drastic changes in properties on the slightest change between NC structures. One of such series studied recently is the quantumbox series comprising highly stable NCsAu 28 (SPh-t Bu) 20 , Au 36 (SPh-t Bu) 24 , Au 44 (SPh-t Bu) 28 , and Au 52 (SPh-t Bu) 32 . All these NCs are protected by the same 4-tert-butylbenzenethiolate (SPh-t Bu) ligand and follow the general formula, Au 8n+4 (SPh-t Bu) 4n+8 , where n = 3−6. 23 The growth pattern in this quantum-box series of NCs can be understood through a
Electrocatalytic hydrogen evolution reaction (HER) holds grip as a promising strategy to obtain renewable energy resources in the form of clean fuel - hydrogen (H2). However, understanding the catalytic mechanism...
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