Unknown

Dataset Information

0

Supramolecular chirality transformation driven by monodentate ligand binding to a coordinatively unsaturated self-assembly based on C 3-symmetric ligands.


ABSTRACT: Monodentate ligand binding is facilitated by supramolecular chirality transformations from propeller-shaped chirality into single-twist chirality by altering the self-assembly of C 3-symmetric chiral ligands. The C 3-symmetric chiral ligands (Im R 3Bz and Im S 3Bz) 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 C 3-symmetric chiral ligands assemble, in a stepwise manner, into a propeller-shaped assembly with a general formula (Im( R or S ) 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 R 3Bz)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 R 3Bz)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.

SUBMITTER: Imai Y 

PROVIDER: S-EPMC6471804 | biostudies-other | 2019 Apr

REPOSITORIES: biostudies-other

altmetric image

Publications

Supramolecular chirality transformation driven by monodentate ligand binding to a coordinatively unsaturated self-assembly based on <i>C</i> <sub>3</sub>-symmetric ligands.

Imai Yuki Y   Yuasa Junpei J  

Chemical science 20190305 15


Monodentate ligand binding is facilitated by supramolecular chirality transformations from propeller-shaped chirality into single-twist chirality by altering the self-assembly of <i>C</i> <sub>3</sub>-symmetric chiral ligands. The <i>C</i> <sub>3</sub>-symmetric chiral ligands (<b>Im <i><sup>R</sup></i> <sub>3</sub>Bz</b> and <b>Im <i><sup>S</sup></i> <sub>3</sub>Bz</b>) contain three chiral imidazole side arms (Im <sup><i>R</i></sup>  and Im <sup><i>S</i></sup> ) at the 1,3,5-positions of a cen  ...[more]

Similar Datasets

| S-EPMC2765196 | biostudies-literature
| S-EPMC2895422 | biostudies-literature
| S-EPMC5878180 | biostudies-literature
| S-EPMC7756587 | biostudies-literature
| S-EPMC5827968 | biostudies-literature
| S-EPMC2674759 | biostudies-literature
| S-EPMC5805703 | biostudies-literature
| S-EPMC9728572 | biostudies-literature
| S-EPMC1360519 | biostudies-literature
| S-EPMC2621067 | biostudies-literature