Bpytrisalen/Bpytrisaloph: A Triangular Platform That Spatially Arranges Different Multiple Labile Coordination Sites.

Complexes that possess multiple metals in their proximity exert useful functions such as multivalent capture and catalytic activities. However, it is often challenging to arrange multiple metals with regular distances and to maintain the reactive coordination sites. We have now designed and synthesized organic macrocyclic ligands, bpytrisalen and bpytrisaloph, as platforms to spatially arrange different kinds of metals and their coordination sites. Metals coordinating to the bpy N units of the triangular ligands are assembled in the cavity with their labile coordination sites directed inward. Meanwhile, the metals at the salen/saloph NO units have axial coordination sites that are vertically pointing out of the triangle. As a result, planar homo- and heterohexanuclear complexes with different kinds of coordination sites are obtained. Furthermore, a double-decker structure was selectively constructed upon coordinating a ditopic linker ligand to the axial coordination sites of the salen units, which shows the orthogonality of the coordination sites at the bpy and salen units. The consistency in the array of metal centers and their coordination sites irrespective of the elements is a desirable feature in the pursuit of applications for the multinuclear complexes.