Self-Assembly and Catalytic Reactivity of BINOL-Bridged Bis(phenanthroline) Metallocages
Self-Assembly and Catalytic Reactivity of BINOL-Bridged Bis(phenanthroline) Metallocages
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DOI：
10.1021/acs.inorgchem.7b02540
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发表时间：
2018-04-02
影响因子：
4.6
通讯作者：
Chan, Yi-Tsu
中科院分区：
文献类型：
--
作者：
Cheng, Kai-Yu;Wang, Shi-Cheng;Chan, Yi-Tsu
用 Zn-II 离子处理后，一系列 BINOL 桥联双（菲咯啉）配体自组装成 [M2L3] 金属定位体，并通过 NMR 光谱和 ESI-MS 光谱仔细表征。其中，BINOL桥联双(菲咯啉)的外消旋混合物经历了手性自分选，提供了两种纯手性金属定位。在具有不同连接位置的异构双（菲咯啉）的络合反应中观察到金属定位的自恋自排序过程。此外，内羟基功能化金属基体[Zn-2{(S)-L-2(OH)}(3)]对芳香族三甲醛与丙二腈的Knoevenagel缩合反应表现出催化活性和底物选择性。
Upon treatment with Zn-II ions, a series of BINOL-bridged bis(phenanthroline) ligands was self-assembled into [M2L3] metallocages, which were carefully characterized by NMR spectroscopy and ESI-MS spectrometry. Among them, a racemic mixture of the BINOL-bridged bis(phenanthrolines) underwent chiral self-sorting to afford two homochiral metallocages. The narcissistic self-sorting process of the metallocages was observed in the complexation reaction of the constitutionally isomeric bis(phenanthrolines) with varying connection positions. Moreover, the endo hydroxyl-functionalized metallocage [Zn-2{(S)-L-2(OH)}(3)] exhibited catalytic activity and substrate selectivity for the Knoevenagel condensation reactions of aromatic tricarbaldehydes with malononitrile.