Coordination-Driven Self-Assembled ZnII6-LnIII3 Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc–
Coordination-Driven Self-Assembled ZnII6-LnIII3 Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc–
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基于水杨酰胺亚胺配体的配位驱动自组装 ZnII6-LnIII3 金属环：合成、结构和 OAc 诱导的选择性发光增强
DOI：
10.1021/acs.inorgchem.8b01525
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发表时间：
2018
影响因子：
4.6
通讯作者：
Wei sheng Liu
中科院分区：
文献类型：
--
作者：
Xue Qin Song;Cai Yun Wang;Huan Huan Meng;Ali Alhafeez Abdulrheem Shamshoom;Wei sheng Liu
通过配位驱动的自组装策略，合成了5个基于水杨酰胺亚胺多齿不对称配体H2 L [1-（2-羟基-3-甲氧基苯甲酰氨基）-2-（2-羟基-3-甲氧基苯亚甲基氨基）乙烷]的ZnII 6-LnII 3杂金属大环化合物.单晶X射线衍射分析表明，这五种金属环是同构的，分子式为[Zn 6Ln 3L 6（OH）2（NO3）4（H2O）]·3 NO3·nCH 3CN（ZnLn-1，其中Ln = Pr、Nd、Eu、Tb或Yb;对于ZnPr-1，n= 4;对于ZnNd-1、ZnEu-1和ZnTb-1，n= 2;对于ZnYb-1，n= 3），其中六个八齿配体L2-和两个原位形成的μ2-OH-离子将ZnII-LnIII-ZnII亚基桥接成一个大环。沿着结构的新奇，ZnNd-1在加入乙酸乙酯后，在可见光和近红外范围内显示出明显的增强发射。基于紫外-可见光谱、核磁共振氢谱、单晶X射线衍射和高分辨电喷雾质谱，我们推测这种发光增强可能是由于TICT的协同效应和由OAc桥联引起的μ2-OH-的无辐射跃迁。我们的研究结果表明，含钕III的杂金属大环可以作为一个主机的阴离子交换，并提供了一个很好的例子，杂金属大环有趣的性质和潜在的应用。
Five heterometallic ZnII6-LnIII3macrocycles based on a salicylamide imine multidentate unsymmetrical ligand H2L [1-(2-hydroxy-3-methoxy-benzamido)-2-(2-hydroxy-3-methoxy-benzylideneamino)-ethane] have been prepared via a coordination-driven self-assembly strategy. Single-crystal X-ray diffraction analysis reveals that the five metallocycles are isomorphic with a formula of [Zn6Ln3L6(OH)2(NO3)4(H2O)]·3NO3·nCH3CN (ZnLn-1, where Ln = Pr, Nd, Eu, Tb, or Yb; forZnPr-1,n= 4; forZnNd-1,ZnEu-1, andZnTb-1,n= 2; forZnYb-1,n= 3), where six octadentate ligands L2–and two in situ-formed μ2-OH–ions bridged the alternating ZnII-LnIII-ZnIIsubunits into a macrocycle. Along with the structural novelty,ZnNd-1shows distinctive enhanced emission in the visible and near-infrared range upon addition of OAc–. On the basis of ultraviolet–visible spectroscopy,1H nuclear magnetic resonance, single-crystal X-ray diffraction, and high-resolution electrospray ionization mass spectrometry, we deduced that this emission enhancement could be attributed to the synergistic effect of TICT and the absent nonradiative transition of μ2-OH–induced distinctively by OAc–bridging. Our results demonstrate that the NdIII-containing heterometallic macrocycle can act as a host for anion exchanging and provide a nice example of heterometallic macrocycles with interesting properties and potential applications.