Supramolecular chirality transformation driven by monodentate ligand binding to a coordinatively unsaturated self-assembly based on C3-symmetric ligands.


Department of Applied Chemistry , Tokyo University of Science , 1-3, Kagurazaka, Shinjuku , Tokyo 162-8601 , Japan . Email: [Email]


Monodentate ligand binding is facilitated by supramolecular chirality transformations from propeller-shaped chirality into single-twist chirality by altering the self-assembly of C3-symmetric chiral ligands. The C3-symmetric chiral ligands (Im R3Bz and Im S3Bz) contain three chiral imidazole side arms (Im R  and Im S ) at the 1,3,5-positions of a central benzene ring. Upon coordination to zinc ions (Zn2+), which have a tetrahedral coordination preference, the C3-symmetric chiral ligands assemble, in a stepwise manner, into a propeller-shaped assembly with a general formula (Im(RorS)3Bz)4(Zn2+)3. In this structure each Zn2+ ion coordinates to the three individual imidazole side arms. The resulting assembly is formally coordinatively unsaturated (coordination number, n = 3) and capable of accepting monodentate co-ligands (imidazole: ImH2) to afford a coordinatively saturated assembly [(ImH2)3(Im R3Bz)4(Zn2+)3]. The preformed propeller-shaped chirality is preserved during this transformation. However, an excess of the monodentate co-ligand (ImH2/Zn2+ molar ratio of ∼1.7) alters the propeller-shaped assembly into a stacked dimer assembly [(ImH2) m (Im R3Bz)2(Zn2+)3] (m = 4-6) with single-twist chirality. This switch alters the degree of enhancement and the circular dichroism (CD) pattern, suggesting a structural transition into a chiral object with a different shape. This architectural chirality transformation presents a new approach to forming dynamic coordination-assemblies, which have transformable geometric chiral structures.