Atom-precise metal nanoclusters, which contain a few tens to hundreds of atoms, have drawn significant interest due to their interesting physicochemical properties. Structural analysis reveals a fundamental architecture characterized by a central core or kernel linked to a staple motif with metal-ligand bonding playing a pivotal role. Ligands not only protect the surface but also exert a significant influence in determining the overall assembly of the larger superstructures. The assemblies of nanoclusters are driven by weak interaction between the ligand molecules; it also depends on the ligand type and functional group present. Here, we report an achiral ligand and Ag(I)···Ag(I) interaction-driven spontaneous resolution of silver-thiolate structure, [Ag18(C6H11S)12(CF3COO)6(DMA)2], where silver atoms and cyclohexanethiolate are connected to form a one-dimensional chain with helicity. Notably, silver atoms adopt different types of coordination modes and geometries. The photoluminescence properties of the one-dimensional (1D) chain structure were investigated, and it was found to exhibit excitation-dependent emission properties attributed to hydrogen-bonding interactions. Experimental and theoretical investigations corroborate the presence of triplet-emitting ligand-to-metal charge-transfer transitions.