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Switching Dual Catalysis without Molecular Switch: Using A Multicomponent Information System for Reversible Reconfiguration of Catalytic Machinery
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-09-19 , DOI: 10.1021/jacs.9b07737
Abir Goswami , Thomas Paululat , Michael Schmittel

Different from the current paradigms of chemistry, a switchable catalytic system is presented that does not rely on a molecular switch in different toggling states but on a smart seven-component mixture that manages the reversible ON/OFF regulation of two catalytic processes. Hereunto, the workflow of two multicomponent rotary catalytic machineries was interlinked by the simultaneous shuffling of two components (metal and ligand) requiring perfect signaling in a 13-component system (see Movie 1). This network underwent reversible switching over three cycles as demonstrated by 1H NMR, UV-vis, and fluorescence spectroscopies and electrospray ionization mass spectrometry. Addition and removal of zinc(II) ions trigger three distinct events in parallel: the (i) mutually dependent self-assembly of three-component nanorotors and two-component reservoirs by resorting components, (ii) toggling between vastly different rotational exchange rates in the self-assembled rotors that directly affect catalysis, and (iii) toggling between two diverse catalytic reactions in a fully reproducible manner. Because of this information system, the concentrations of free aza-crown ether 7 and its complex with copper(I), that is, [Cu(7)]+, which represent the effective catalysts, are up- and downregulated in a manner to alternately switch ON/OFF a catalytic conjugate addition and a click reaction.

中文翻译:

在没有分子开关的情况下切换双催化:使用多组分信息系统进行催化机械的可逆重新配置

与当前的化学范式不同,本文提出了一种可切换的催化系统,它不依赖于不同切换状态的分子开关,而是依赖于管理两个催化过程的可逆开/关调节的智能七组分混合物。在此之前,两个多组分旋转催化机器的工作流程通过在 13 组分系统中需要完美信号的两种组分(金属和配体)的同时改组而相互关联(参见电影 1)。该网络经历了三个循环的可逆切换,如 1H NMR、UV-vis、荧光光谱和电喷雾电离质谱所证明的那样。添加和去除锌 (II) 离子会同时触发三个不同的事件:(i) 三组分纳米转子和二组分储层的相互依赖的自组装,通过不同的组分,(ii) 在直接影响催化作用的自组装转子中切换非常不同的旋转交换率,以及 (iii) 在两者之间切换以完全可重复的方式进行两种不同的催化反应。由于该信息系统,代表有效催化剂的游离氮杂冠醚 7 及其与铜 (I) 的络合物的浓度,即 [Cu(7)]+ 以某种方式上调和下调交替打开/关闭催化共轭添加和点击反应。(iii) 以完全可重复的方式在两种不同的催化反应之间切换。由于该信息系统,代表有效催化剂的游离氮杂冠醚 7 及其与铜 (I) 的络合物的浓度,即 [Cu(7)]+ 以某种方式上调和下调交替打开/关闭催化共轭添加和点击反应。(iii) 以完全可重复的方式在两种不同的催化反应之间切换。由于该信息系统,代表有效催化剂的游离氮杂冠醚 7 及其与铜 (I) 的络合物的浓度,即 [Cu(7)]+ 以某种方式上调和下调交替打开/关闭催化共轭添加和点击反应。
更新日期:2019-09-19
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