Xie Jia-Nan, Li Yun-Lan, Wang Hai-Ling, Xiao Zi-Xin, Zhu Zhong-Hong, Liang Fu-Pei, Zou Hua-Hong
School of Chemistry and Pharmaceutical Sciences, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guangxi Normal University, Guilin 541004, P. R. China.
Dalton Trans. 2024 Mar 19;53(12):5665-5675. doi: 10.1039/d3dt03314g.
The complex hydrolysis process and strong uncertainty of self-assembly rules have led to the precise synthesis of lanthanide clusters still being in the "blind-box" stage and simplifying the self-assembly process and developing reliable regulation strategies have attracted widespread attention. Herein, different anions are used to induce the construction of a series of dysprosium clusters with different shapes and connections. When the selected anion is NO, it blocks the coordination of metal sites around the cluster through the terminal group coordination mode, thereby controlling the growth of the cluster. When NO was changed to OAc, OAc adopted a bridging mode to induce modular units to build dysprosium clusters through an annular growth mechanism. Specifically, we selected 2-amino-6-methoxybenzoic acid, 2-hydroxybenzaldehyde, and Dy(NO)·6HO to react under solvothermal conditions to obtain a pentanuclear dysprosium cluster (1). The five Dy(III) ions in 1 are distributed in upper and lower planes and are formed by the tight connection of nitrogen and oxygen atoms, and μ-OH bridges on the ligand. Next, octa-nuclear dysprosium cluster (2) were obtained by only regulating ligand substituents. The eight Dy(III) ions in 2 are tightly connected through ligand oxygen atoms, μ-OH, and μ-OH bridges, forming an elliptical {Dy/O} cluster core. Furthermore, only by changing NO to OAc, a wheel-shaped tetradeca-nuclear dysprosium cluster (3) was obtained. Cluster 3 is composed of OAc bridged multiple template DyL units and pulling of these template units connected by an annular growth mechanism forms a wheel-shaped cluster. The angle of the coordination site on NO is ∠ONO = 115°, which leads to the further extension of the metal sites on the periphery of clusters 1 and 2 through the terminal group coordination mode, thereby regulating the structural connection of the clusters. However, the angle of the coordination site on OAc is ∠OCO = 128°, and a slightly increased angle leads to the formation of a ring-shaped cluster 3 by connecting the template units through bridging. This is a rare example of the controllable construction of lanthanide clusters with different shapes induced by the regulation of different anions, which provides a new method for the precise construction of lanthanide clusters with special shapes.
复杂的水解过程和自组装规则的强烈不确定性导致镧系元素簇的精确合成仍处于“盲盒”阶段，简化自组装过程并开发可靠的调控策略已引起广泛关注。在此，使用不同的阴离子诱导构建一系列具有不同形状和连接方式的镝簇。当选择的阴离子为NO时，它通过端基配位模式阻断簇周围金属位点的配位，从而控制簇的生长。当将NO改为OAc时，OAc采用桥连模式，通过环状生长机制诱导模块化单元构建镝簇。具体而言，我们选择2-氨基-6-甲氧基苯甲酸、2-羟基苯甲醛和Dy(NO)·6HO在溶剂热条件下反应，得到一个五核镝簇(1)。1中的五个Dy(III)离子分布在上下平面，由氮和氧原子以及配体上的μ-OH桥紧密连接形成。接下来，仅通过调节配体取代基得到八核镝簇(2)。2中的八个Dy(III)离子通过配体氧原子、μ-OH和μ-OH桥紧密连接，形成一个椭圆形的{Dy/O}簇核。此外，仅将NO改为OAc，就得到了一个轮状的十四核镝簇(3)。簇3由OAc桥连多个模板DyL单元组成，这些模板单元通过环状生长机制连接并拉动形成一个轮状簇。NO上配位点的角度为∠ONO = 115°，这导致簇1和2外围的金属位点通过端基配位模式进一步延伸，从而调节簇的结构连接。然而，OAc上配位点的角度为∠OCO = 128°，角度略有增加导致通过桥连连接模板单元形成环状簇3。这是通过不同阴离子调控诱导可控构建不同形状镧系元素簇的罕见例子，为精确构建具有特殊形状的镧系元素簇提供了一种新方法。
