Capturing the Trajectory of Metal-Ion-Cluster Formation: Stepwise Accumulation of Zn(II) Ions in a Robust Coordination Space Formed by a Rigid Tridentate Carboxylate Ligand
英文:
Capturing the Trajectory of Metal-Ion-Cluster Formation: Stepwise Accumulation of Zn(II) Ions in a Robust Coordination Space Formed by a Rigid Tridentate Carboxylate Ligand
Organic ligand-directed synthesis of metal-ion clusters with a well-defined number and arrangement of metal ions is an important subject toward the development of functional inorganic–organic nanohybrids. Here we report the synthesis of multinuclear Zn–oxo clusters using a triptycene-based rigid ligand (H3L) featuring three metal-coordination sites arranged in a triangular shape. Upon complexation of H3L with zinc acetate dihydrate, a decanuclear Zn–oxo cluster and multinuclear Zn–oxo clusters with a smaller number of Zn(II) ions were formed as the final product and its intermediates, respectively. A comparison of the X-ray structure of the final product with those of the intermediates revealed the cluster-formation process, where four triptycene ligands preorganize to form a robust coordination space to which Zn(II) ions accumulate in a stepwise manner. This stepwise metal-ion accumulation, along with the formation of a large tetrahedral decanuclear Zn–oxo cluster, highlights the potential of ligand design using 1,8,13-substituted triptycenes for the development of various metal-ion clusters.
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