Metallo‐Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination
Metallo‐Helicoid with Double Rims: Polymerization Followed by Folding by Intramolecular Coordination
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DOI：
10.1002/ange.202010696
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发表时间：
2020-11
影响因子：
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通讯作者：
Guangqiang Yin;S. Kandapal;Chung-Hao Liu;Heng Wang;Jianxiang Huang;Shu‐Ting Jiang;Tan Ji;Yu Yan;Sandra Khalife;Ruhong Zhou;Libin Ye;Bingqian Xu;Hai‐Bo Yang;M. Nieh;Xiaopeng Li
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作者：
Guangqiang Yin;S. Kandapal;Chung-Hao Liu;Heng Wang;Jianxiang Huang;Shu‐Ting Jiang;Tan Ji;Yu Yan;Sandra Khalife;Ruhong Zhou;Libin Ye;Bingqian Xu;Hai‐Bo Yang;M. Nieh;Xiaopeng Li
在本研究中，我们建立了一种可行的策略，通过共价聚合和分子内配位驱动的自组装相结合来构建具有螺旋结构的新型金属聚合物。在该设计中，制备了四配位单体（M），其中两个末端炔在外缘用于聚合，两个三联吡啶（TPY）在内缘用于随后通过选择性分子内配位进行折叠。然后，通过Glaser-Hay偶联反应，通过聚合M来合成线性共价聚合物（P）。最后，TPYs与Zn（II）的分子内配位作用使P的骨架折叠成具有双边缘的右旋或左旋金属螺旋体（H）。双链DNA分子（dsDNA）由于螺旋体内缘带多个正电荷，可通过静电相互作用与H发生相互作用。值得注意的是，双链DNA允许通过手性诱导的方式排他性地形成右手性的H。
In this study, we established a feasible strategy to construct a new type of metallo‐polymer with helicoidal structure through the combination of covalent polymerization and intramolecular coordination‐driven self‐assembly. In the design, a tetratopic monomer (M) was prepared with two terminal alkynes in the outer rim for polymerization, and two terpyridines (TPYs) in the inner rim for subsequent folding by selective intramolecular coordination. Then, the linear covalent polymer (P) was synthesized by polymerization ofMvia Glaser‐Hay homocoupling reaction. Finally, intramolecular coordination interactions between TPYs and Zn(II) folded the backbone ofPinto a right‐ or left‐handed metallo‐helicoid (H) with double rims. Owing to multiple positive charges on the inner rim of helicoid, double‐stranded DNA molecules (dsDNA) could interact withHthrough electrostatic interactions. Remarkably, dsDNA allowed exclusive formation ofHwith right handedness by means of chiral induction.