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The atomically precise metal nanoclusters (NCs) have attracted significant attention due to their superatomic behavior originating from the quantum confinement effect. This behavior makes these materials suitable for various photoluminescence-based applications, including chemical sensing, bioimaging, and phototherapy, owing to their intriguing optical properties. Especially, the manipulation of inter- or intracluster interaction through cluster-assembled materials (CAMs) presents significant pathways for modifying the photophysical properties of NCs. Herein, two distinct CAMs, Au25–Zn-Hex and Au25–Zn-Rod, were synthesized via forming a coordination bond between Au25(p-HMBA)18− (p-H2MBA = 4-mercaptobenzoic acid) and Zn2+. Au25–Zn-Rod exhibited a 6-fold higher luminescence intensity in the near-infrared region compared to Au25–Zn-Hex, attributed to synergistic inter- and intracluster interactions that induce exciton delocalization and structure rigidification at the atomic scale. This study highlights the potential of diverse lattice symmetries in cluster-based frameworks for tuning the photophysical properties, contributing to a deeper understanding of the structure–property relationship in Au NCs.
Kim et al. (2024) studied this question.