Synthesis and mechanochemical inertness of a Zn ( II ) bidipyrrin double helix
Synthesis and mechanochemical inertness of a Zn ( II ) bidipyrrin double helix
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DOI：
10.1002/pol.20220579
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发表时间：
2022-11
影响因子：
3.4
通讯作者：
Junfeng Zhou;D. Sathe;Andrew Ciccotelli;Junpeng Wang
中科院分区：
文献类型：
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作者：
Junfeng Zhou;D. Sathe;Andrew Ciccotelli;Junpeng Wang
螺旋结构在生物大分子和手性催化中起着重要的作用。螺旋结构的机械力化学展开在过去几年中引起了化学家的注意。然而，它是有限的，研究如何机械化学反应性的螺旋构型的影响的几个案例。没有报道合成的螺旋机械载体。在本文中，Zn（II）联二吡咯（BDPR-Zn）双螺旋被设计为潜在的机械载体。制备含有双束缚BDPR-Zn的环烯烃并用于开环复分解聚合。对相应的聚合物进行脉冲超声处理，以进行机械化学测试。超声处理结果揭示了BDPR-Zn单元的机械化学惰性，这进一步得到了力耦合模拟的支持。虽然没有观察到明显的激活，但我们对BDPR-Zn单元的初步结果可以启发进一步合理设计力诱导的螺旋解折叠。
Helices are unique structures that play important roles in biomacromolecules and chiral catalysis. The mechanochemical unfolding of helical structures has attracted the attention of chemists in the past few years. However, it is limited to a few cases which investigated how the mechanochemical reactivity is impacted by helical configurations. No synthetic helical mechanophore is reported. Herein, a Zn (II) bidipyrrin (BDPR‐Zn) double helix is designed as a potential mechanophore. A cyclic olefin containing a doubly strapped BDPR‐Zn is prepared and used for ring‐opening metathesis polymerization. The corresponding polymer is subjected to pulsed ultrasonication for mechanochemical testing. The sonication results reveal the mechanochemical inertness of BDPR‐Zn unit, which is further supported by force‐coupled simulation. Although no obvious activation is observed, our preliminary results on BDPR‐Zn unit could inspire further rational designs on force‐induced helix unfolding.