A comprehensive review of atomically precise metal nanoclusters with emergent photophysical properties towards diverse applications

Atomically precise metal nanoclusters (MNCs) composed of a few to hundreds of metal atoms represent an emerging class of nanomaterials with a precise composition. With the size approaching the Fermi wavelength of electrons, their energy levels are well-separated, leading to molecule-like properties, like discrete single electronic transitions, tunable photoluminescence (PL), inherent structural anisotropy, and distinct redox behavior. Extensive synthetic efforts and electronic structure revelation have expanded applicability of MNCs in catalysis, optoelectronics, and biology. This review highlights the intriguing photophysical and electrochemical behaviors of MNCs and their regulatory parameters and applications. Initially, we present a brief discussion on the evolution of MNCs from gas-phase naked metal clusters to monolayer ligand-protected MNCs along with representative studies on their electronic structure. Due to their quantized molecular orbitals, they often exhibit PL, which can be regulated based on their capping ligands, number of atoms, crystal packing, presence of heterometal, and surrounding environment. Apart from PL, the relaxation pathways of MNCs on an ultrafast time scale have been extensively studied, which significantly differ from that of plasmonic metal nanoparticles. Moreover, their interaction with high-intensity light results in unique non-linear optical properties. The synergy between MNCs in a hierarchical self-assembled structure has been exploited to enhance their PL by precisely tuning their non-covalent interactions. Moreover, several NC-based hybrids have been designed to exhibit efficient electron or energy transfer in the photoexcited state. In the next section, we briefly focus on the redox behavior of NCs and facile electron transfer to suitable substrates, which result in enzyme-like catalytic activity. Utilizing these photophysical and electrochemical behaviors, NCs are widely employed in catalysis, optical sensing, and light-harvesting applications, which are also discussed in this review. In the final section, conclusions and open questions for the NC research community are included. This review will provide a comprehensive view of the emerging physicochemical properties of MNCs, thereby enabling an understanding for their precise modulation in future.