Heterometallic coordination compounds that contain more than one kind of metal ions and their supramolecular aggregates have attracted considerable attention in the fields of coordination chemistry and supramolecular chemistry. This class of compound is commonly synthesized by the one-step self-assembly of well-designed organic ligands in combination with a mixture of metal ions, which often results in the formation of undesired products. To overcome this issue, we have developed a metalloligand approach, in which a pre-designed metal complex with several donor sites is stepwise reacted with metal ions.¹ For example, we have shown that [Au(D-pen-S)₂]^3- (H_2pen = penicillamine) acts as a multidentate metalloligand to produce a variety of heterometallic coordination compounds. Recently, this monogold(I) metalloligand system was extended to digold(I) and trigold(I) systems by introducing a digold(I)/trigold(I) linker with diphosphine/triphosphine ligands.² Here we present the coordination functionality of these metalloligands, which lead to the construction of unique metallosupramolecular architectures. References 1. a) Oji, K.; Igashira-Kamiyama, A.; Yoshinari, N.; Konno, T. Angew. Chem. Int. Ed. 2014, 53, 1992-1996; b) Yoshinari, N.; Kakuya, A.; Lee, R.; Konno, T. Bull. Chem. Soc. Jpn. 2015, 88, 59-68; c) Surinwong, S.; Yoshinari, N.; Kojima, T.; Konno, T. Chem. Commun. 2016, 52, 12893-12896; d) Kuwamura, N.; Kurioka, Y.; Konno, T. Chem. Commun. 2017, 53, 846-849; e) Kouno, M.; Yoshinari, N.; Kuwamura, N.; Yamagami, K.; Sekiyama, A.; Okumura, A.; Konno, T. Angew. Chem. Int. Ed. 2017, 56, 13762-13766. 2. a) Yamada, M.; Yoshinari, N.; Kuwamura, N.; Saito, T.; Harano, K.; Nakamura, Sekiyama, A.; Suenobu, T.; Yamada, Y.; Konno, T.; Chem. Sci., 2017, 8, 384-386; b) Itai, T.; Kojima, T.; Kuwamura, N.; Konno, T. Chem. Eur. J. 2017, 23, 16438-16441; c) Yamashita, S.; Nakazawa, Y.; Yamanaka, S.; Okumura, M.; Kojima, T. Konno, T., Sci. Rep. 2018, 8, 2606.