Geometric adventures with self-assembled metal-ligand coordination structuresTools Fan, Yucong (2024) Geometric adventures with self-assembled metal-ligand coordination structures. MRes thesis, University of Nottingham.
AbstractDynamic covalent chemistry (DCC) has become of increasing interest to researchers due to its unique properties in constructing complex three-dimensional structures. Metal-ligand coordination interactions have been used extensively to construct three-dimensional structures due to the well-defined coordination preferences of metal ions. In this work, two linear tridentate ditopic ligands with different side arms; and two tridentate tritopic ligands with a triangular shape, (one with a benzene at its centre and one with a triazine) were used to coordinate with the transition metal ions Fe2+ and Zn2+. The ligands have the same denticity and topicity, however, the self-assembly products of them were different. The linear ligand with the side group further away had the same behaviour when coordinated with Fe2+ and Zn2+. Both Fe2+ and Zn2+ gave two self-assembly products, which were M4L4 squares and M3L3 triangles, presumed to be circular helicates. The other linear ligand with a side group closer to coordination sites was only investigated with Fe2+, where it gave M4L4 squares and M3L3 triangles on self-assembly. Both the triangular ligands gave interesting results with both Fe2+ and Zn2+ ions. Both triangular ligands gave an M6L4 structure (presumed octahedral) and an M9L6 structure (presumed triaugmented triangular prism) with Fe2+ ions. With Zn2+ ions, the ligand with benzene at its centre only gave M6L4 structures (presumed octahedral); the ligand with triazine at its centre gave both an M6L4 structure (presumed octahedral) and an M9L6 structure (presumed triaugmented triangular prism). In this work however, the influence of side arms on the linear ligands still needs further investigation. Future work will also study different metal ions with different coordination geometries.
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