Anionic Templates Drive Conversion between a Zn(II)(9)L(6) Tricapped Trigonal Prism and Zn(II)(6)L(4) Pseudo-Octahedra

[Image: see text] This work introduces the use of 8-aminoquinoline subcomponents to generate complex three-dimensional structures. Together with a tris(formylpyridine), 8-aminoquinoline condensed around Zn(II) templates to produce a tris(tridentate) ligand. This ligand is incorporated into either a tricapped trigonal prismatic Zn(II)(9)L(6) structure or a pair of pseudo-octahedral Zn(II)(6)L(4) diastereomers, with S(4) and D(2) symmetries. Introduction of a methyl group onto the aminoquinoline modulated the coordination sphere of Zn(II), which favored the Zn(II)(9)L(6) structure and disfavored the Zn(II)(6)L(4) assembly. The tricapped trigonal prismatic Zn(II)(9)L(6) architecture converted into a single Zn(II)(6)L(4) cage diastereomer following the addition of a dianionic 4,4′-dinitrostilbene-2,2′-disulfonate guest. Four of these guests clustered tightly at the four windows of the Zn(II)(6)L(4) cage, held in place through electrostatic interactions and hydrogen bonding, stabilize a single diastereomeric configuration with S(4) symmetry.