Abstract
Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications.
Highlights
The structural control and morphological evolution of the directed self-assembly can be controlled by the nanoscale forces such as dipolar attraction, van der Waals interactions, electrostatic interactions, π–π stacking, metallophilic interactions, etc
Different types of nanoscale forces such as dipolar interactions, van der Waals interactions, electrostatic interactions, hydrogen bonding, C–H···π interaction, π–π stacking, metallophilic interactions, and amphiphilicity along with the external triggers are responsible for directed self-assembly process of metal nanoclusters (MNCs)
The quantum chemistry approach should bridge the gap to address the photophysical properties of MNCs embedded in self-assembly
Summary
The study of self-assembly of nanomaterials has been an efficient and powerful strategy in nanotechnology for decades and is still relevant today. The richness of surface ligands in MNCs and the versatile surface functionalities allow for elaborating strategies involving manipulating the driving forces guiding the intercluster interactions These attractive forces act as a glue between surface ligands of different NCs and can be triggered by external stimuli such as metal ions, pH, macromolecules, solvents, light, etc. The origin of the photoluminescence (PL), in particular in the near-infrared, from thiolate-protected gold nanoclusters remains elusive It is still a major challenge for researchers to map out a definitive relationship between the atomic structure and the PL property and understand how the metal core (through excitations via the Au(0) kernel) and. Building a massive assembly of NCs onto higher-order hybrid superstructures will lead to strong confinement on many length scales This confinement will reduce the solvent accessibility, increasing the aggregationinduced emission (AIE) process of luminescent MNC-based assemblies. The impacts of the different forces on the AIE process of MNC-based assemblies will be discussed
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