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
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
复制标题
捕获金属离子簇形成的轨迹：Zn(II) 离子在刚性三齿羧酸配体形成的鲁棒配位空间中逐步积累
DOI：
10.1021/acs.inorgchem.1c03758
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发表时间：
2022
影响因子：
4.6
通讯作者：
Fukushima Takanori
中科院分区：
文献类型：
--
作者：
Kato Mikiya;Fukui Tomoya;Sato Hiroyasu;Shoji Yoshiaki;Fukushima Takanori
有机配体定向合成具有明确金属离子数量和排列的金属离子簇是发展功能无机-有机纳米杂化的重要课题。在这里，我们报道了使用三烯基刚性配体（H3L）合成多核锌氧簇的方法，该配体具有三角形排列的三个金属配位位点。H3L与二水合乙酸锌络合后，最终产物为十核Zn - oxo簇，中间产物为含有较少Zn（II）离子的多核Zn - oxo簇。最终产物的x射线结构与中间体的x射线结构的比较揭示了团簇形成过程，其中四个三烯配体预先组织形成一个强大的配位空间，Zn（II）离子以逐步的方式积聚在其中。这种金属离子的逐步积累，以及一个大的四面体十核锌氧簇的形成，突出了利用1,8,13取代三烯设计配体以发展各种金属离子簇的潜力。
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.