A Toggle Nanoswitch Alternately Controlling Two Catalytic Reactions

A Toggle Nanoswitch Alternately Controlling Two Catalytic Reactions
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DOI:
10.1002/anie.201408457
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发表时间:
2014-12-15
影响因子:
16.6
通讯作者:
Schmittel, Michael
Schmittel, Michael
中科院分区:
化学1区
文献类型:
--
作者:
De, Soumen;Pramanik, Susnata;Schmittel, Michael

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通过交替加入2-二茂铁基-1,10-菲咯啉(2)和铜(I)离子实现了三角形纳米开关[Cu(1)](+)的两种状态之间的可逆切换。这两种切换状态以完全无干扰的方式调节两种不同催化剂哌啶和[Cu(2)](+)的结合和释放,并允许两个正交催化过程的交替开/关切换。在切换状态I中,哌啶从纳米开关释放并催化4-硝基苯甲醛和丙二酸二乙酯之间的Knoevenagel加成(ON-1和OFF-2),而在状态II中,释放的[Cu(2)](+)催化4-硝基-苯乙炔和苄基叠氮化物之间的点击反应(OFF-1和ON-2)。在向(OFF-1和ON-2)状态添加一当量的2时,两个催化活性过程都被关闭(OFF-1和OFF-2)。
Reversible switching between two states of the triangular nanoswitch [Cu(1)](+) was accomplished by alternate addition of 2-ferrocenyl-1,10-phenanthroline (2) and copper(I) ions. The two switching states regulate the binding and release of two distinct catalysts, piperidine and [Cu(2)](+), in a fully interference-free manner and allow alternating on/off switching of two orthogonal catalytic processes. In switching state I, piperidine is released from the nanoswitch and catalyzes a Knoevenagel addition between 4-nitrobenzaldehyde and diethyl malonate (ON-1 and OFF-2), while in state II the released [Cu(2)](+) catalyzes a click reaction between 4-nitro-phenylacetylene and benzylazide (OFF-1 and ON-2). Upon addition of one equivalent of 2 to the (OFF-1 and ON-2)-state, both catalytically active processes are shut down (OFF-1 and OFF-2).