Multinuclear multibenzimidazole metal complexes frequently exhibit novel structures and properties, and are an example of versatile compounds in bioinorganic chemistry. In this work, first, we synthesized the mononuclear complex [Cu(ntb)(H 2O)] 2+, 1, by using tris[(benzimidazol- 2-yl)methyl]amine (ntb). Then, a library of multicationic ntb-Cu(ii) complexes, 2-9, was prepared by replacing the labile water molecule in 1 with multifunctional carboxylates acting as a bridge linker between two or four ntb-Cu(ii) units under slightly acidic or alkal...