Circular dichroism and circularly polarized luminescence of ligand-protected molecular metal clusters: insights into structure-chiroptical property relationships.

Molecular noble metal clusters are an emerging class of circularly polarized luminescent (CPL) nanomaterials. Many of the ligand-protected metal clusters exhibit discrete electronic absorption bands, which are assigned to their structural components such as metal core, ligands and metal-ligand interfaces. This implies the suitability of the chiroptical spectroscopic approach to unravel the structure-chiroptical property relationships in molecular metal clusters. Due to the tremendous developments in computational methods for investigating chiroptical properties, along with circular dichroism (CD) and CPL spectroscopy, understanding of the structure-chiroptical properties of these clusters is rapidly progressing. This review discusses various strategies such as the use of chiral ligands, metal atom substitution, ligand exchange, co-crystallization with chiral ligands, etc., for inducing and enhancing the CPL of such metal clusters. This review demonstrates the potential of combined CD-CPL spectroscopic investigations and theoretical calculations to unravel the origins of photoluminescence and CPL activity of chiral metal clusters.

A concise guide to chemical reactions of atomically precise noble metal nanoclusters.

Nanoparticles (NPs) with atomic precision, known as nanoclusters (NCs), are an emerging field in materials science in view of their fascinating structure-property relationships. Ultrasmall noble metal NPs have molecule-like properties that make them fundamentally unique compared with their plasmonic counterparts and bulk materials. In this review, we present a comprehensive account of the chemistry of monolayer-protected atomically precise noble metal nanoclusters with a focus on the chemical reactions, their diversity, associated kinetics, and implications. To begin with, we briefly review the history of the evolution of such precision materials. Then the review explores the diverse chemistry of noble metal nanoclusters, including ligand exchange reactions, ligand-induced structural transformations, and reactions with metal ions, metal thiolates, and halocarbons. Just as molecules do, these precision materials also undergo intercluster reactions in solution. Supramolecular forces between these systems facilitate the creation of well-defined hierarchical assemblies, composites, and hybrid materials. We conclude the review with a future perspective and scope of such chemistry.

Analytical separation techniques: toward achieving atomic precision in nanomaterials science.

The size- and shape-dependence of the properties are the most characteristic features of nanoscale matter. In many types of nanomaterials, there is a size regime wherein every atom counts. In order to fully realize the idea of 'maneuvering things atom by atom' envisioned by Richard Feynman, synthesis and separation of nanoscale matter with atomic precision are essential. It is therefore not surprising that analytical separation techniques have contributed tremendously toward understanding the size- as well as shape-dependent properties of nanomaterials. Fascinating properties of nanomaterials would not have been explored without the use of these techniques. Here we discuss the pivotal role of analytical separation techniques in the progress of nanomaterials science. We begin with a brief overview of some of the key analytical separation techniques that are of tremendous importance in nanomaterials research. Then we describe how each of these techniques has contributed to the advancements in nanomaterials science taking some of the nanosystems as examples. We discuss the limitations and challenges of these techniques and future perspectives.

Gold-Doping Effect on Two-Photon Absorption and Luminescence of Atomically Precise Silver Ligated Nanoclusters.

Noble metal nanoclusters allow for the atomically-precise control of their composition. However, to create nanoclusters with pre-defined optical properties, comprehensive description of their structure-property relation is required. Here, we report the gold atom doping impact on one-photon and two-photon absorption (TPA) and luminescence properties of ligated silver nanoclusters via combined experimental studies and time-dependent density functional theory simulations (TD-DFT). We synthesized a series of Ag25-x Aux (DMBT)18 nanoclusters where x=0, 1 and 5-10. For Ag24 Au1 (DMBT)18 we demonstrate that the presence of the central Au dopant strongly influences linear and non-linear optical properties, increasing photoluminescence quantum yield and two-photon brightness, with respect to undoped silver nanoclusters. With improved TPA and luminescence, atomically-precise AuAg alloys presented in our work can serve as robust luminescent probes e.g. for bioimaging in the second biological window.