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, Au-25-Zn-Hex and Au-25-Zn-Rod, were synthesized via forming a coordination bond between [Au-25(p-HMBA)(18)](-) (p-H(2)MBA = 4-mercaptobenzoic acid) and Zn2+. Au-25-Zn-Rod exhibited a 6-fold higher luminescence intensity in the near-infrared region compared to Au-25-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.