In this context, to explore alternative methods of linking, research has recently focused on introducing acetylide ligands and their analogs into gold (Au) clusters; the Au clusters are coordinated by diverse types of ligands, such as phosphines and halogens, through ligand exchange reactions. For example, Tsukuda et al. synthesized a building block superatom by exchanging the two terminal chlorine ligands of [Au13(dppe)5Cl2] 3+ (hereafter referred to as 1; dppe = 1,2-bis(diphenylphosphino)ethane) (Table , Fig. ) with terpyridine derivative acetylide ligands (chelating ligands), thereby introducing terpyridine (EPTpy = 4ʹ-(4-ethynylphenyl)-2,2ʹ:6ʹ,2ʺ-terpyridine) at both ends of the Au13 cluster. This exchange Please do not adjust margins Please do not adjust margins subsequently enabled the formation of a one-dimensional polymer upon the addition of transition metal ions into the solution containing building block superatom, wherein the metal ions coordinated with terpyridine, which led to the formation of Au13 cluster-linked polymer chains (Scheme 1A). Additionally, (IrAu12)2L dimers and (IrAu12)3L2 trimers were synthesized using the analogous compound [IrAu12(dppe)5(PA)2] + (PA = phenylacetylide; Fig. ) to control the cleavage of the Au-C bond (dissociation of PA) within the cluster and by introducing diisocyanide linker L, which has isocyano groups at both ends (Scheme 1B). The approach used in Scheme 1A affords the facile synthesis of one-dimensional assemblies by simply introducing transition metal ions. However, controlling the number of linkages is difficult. By contrast, the approach in Scheme 1B allows for control of the number of linkages in the product by combining clusters where PA is dissociated from the clusters, with one PA remaining as an end cap to suppress polymerization. However, the number of strong acid reagents suitable for PA dissociation is limited, which restricts the types of clusters that can be used for linking.