| 基于阴离子的Zn-salen修饰金属-有机笼的构型调控 |
| Effects of anions on the structural regulation of Zn-salen-modified metal-organic cage |
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| 摘要: 选择具有构型可变的手性前体Zn-salen修饰的单齿配体RZn，与辅酶NADH (还原型烟酰胺腺嘌呤二核苷酸)修饰的三齿配体通过3∶1互补组装策略与方形平面配位的Pd(Ⅱ)自组装，实现了混合不同功能配体的手性金属-有机笼Pd-R (Zn)的定向可控构筑。紫外可见光谱和荧光光谱表明，利用对离子与金属-有机主体差异化的主客体静电相互作用，不同阴离子能够选择性作用于Zn-salen修饰金属-有机笼的不同位点，进而实现笼状化合物的构型调控。相比于其他阴离子，氯离子使Pd-R (Zn)的荧光发射增强效应最为显著，同时紫外可见吸收光谱中归属于salen骨架共轭的吸收带降低，且金属至配体电荷转移吸收带发生蓝移。圆二色谱和核磁共振氢谱进一步表明，氯离子的引入有利于产生更刚性的骨架结构。 |
| 关键词: 金属-有机笼 Zn-salen 主客体静电作用 阴离子 构型调控 |
| 基金项目: 国家自然科学基金(No.92361201，22201129)和江苏省自然科学基金(No.BK20220033)资助。 |
| Abstract: By virtue of a 3∶1 complementary coordination strategy, a chiral heteroleptic metal-organic cage that contains divergent functional units, Pd-R(Zn), was precisely constructed via self-assembly of monodentate variational Znsalen ligands RZn and NADH (reduced nicotinamide adenine dinucleotide) mimic modified tridentate ligands with square-planar Pd ions. UV-Vis and luminescence spectra experiments reveal that different anions could selectively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound, by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts. Compared to other anions, the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd-R(Zn), meanwhile, the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease, and the metal-to-ligand induced peak displayed a blue shift effect. Circular dichroism and 1H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold. |
| Keywords: metal-organic cage Zn-salen host-guest electrostatic interaction anions structural regulation |
| 投稿时间：2024-06-03 修订日期：2024-07-05 |
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| 郭乔佳,蔡俊凯,段春迎.基于阴离子的Zn-salen修饰金属-有机笼的构型调控[J].无机化学学报,2024,40(11):2203-2211. |
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