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首页> 外文期刊>Crystal growth & design >Metal Organo-Polymeric Framework via [2+2] Cycloaddition Reaction: Influence of Hydrogen Bonding on Depolymerization Published as part of a Crystal Growth and Design virtual special issue Honoring Prof William Jones and His Contributions to Organic Solid-State Chemistry
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Metal Organo-Polymeric Framework via [2+2] Cycloaddition Reaction: Influence of Hydrogen Bonding on Depolymerization Published as part of a Crystal Growth and Design virtual special issue Honoring Prof William Jones and His Contributions to Organic Solid-State Chemistry

机译：金属有机型聚合物框架通过[2 + 2]环加成反应：氢键在作为晶体生长和设计虚拟特殊问题的一部分发布的解聚对威廉·琼斯教授的影响，以及他对有机固态化学的贡献

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In the doubly interpenetrated metal-organic framework (MOF) structure with cds topology, [Zn-2(bpeb)-(dhbdc)(fa)(2)], 1 (where bpeb = trans,trans,trans-1,4-bis[2-(4'pyridyl)ethenyl]benzene, dhbdc = 2,5-dihydroxy-benzene-1,4-dicarboxylate, and fa = formate), the adjacent bpeb ligands are aligned in a slip-stacked manner infinitely, and the olefin pairs are aligned in parallel ready to undergo a quantitative photochemical [2 + 2] cycloaddition reaction. The single-crystal-to-single-crystal (SCSC) photoreaction under UV light yielded a non-interpenetrated [Zn-2(poly-bppcb)(dhbdc)(fa)(2)], 2 (where poly-bppcb = 1,3-(4,4'-bipyridyl)-2-phenylcyclobutane) in which the poly-bppcb polymer comprising cyclobutane rings are nicely integrated into the two-dimensional coordination polymeric sheet formed by [Zn-2(dhbdc)(fa)(2)]. This organic polymer can be depolymerized back to 1 by heating 2 at 250 degrees C in a hot air oven for 6 h. The cleavage of cyclobutane rings to bpeb ligands has been attributed to the hydrogen bonding of the two hydroxy groups in the dhbdc ligand. In a similar metal organo-polymeric framework with bdc ligand, the poly-bppcb could not be depolymerized. Thus, this study provided some new insights into the reversible cleavage of cyclobutane polymers. These polymeric materials based on cyclobutane may be environmentally benign as these can be depolymerized to yield easily disposable and degradable monomers.
机译：在双渗透金属 - 有机框架（MOF）结构中，具有CDS拓扑，[Zn-2（BPEB） - （DHBDC）（FA）（2）]，1（其中BPEB = Trans，Trans-1,4- BIS [2-（4'-（4'-（4'）乙烯基]苯，DHBDC = 2,5-二羟基 - 苯-1,4-二羧酸酯，以及FA =甲酸酯），相邻的BPEB配体无限地以防滑堆叠的方式排列，烯烃对并联对准，以进行定量光化学[2 + 2]环加成反应。 UV光下的单晶 - 单晶（SCSC）光学反应产生非互渗透[Zn-2（Poly-BPPCB）（DHBDC）（FA）（2）]，2（其中Poly-BPPCB = 1 ，3-（4,4'-双吡啶基）-2-苯基环丁烷，其中包含环丁烷环的多BPPCB聚合物很好地集成到通过[Zn-2（DHBDC）（FA）（ 2）]。通过在250℃的热空气烘箱中加热2，将该有机聚合物在热空气烘箱中加热6小时，可以在250℃下加热回到1。环丁烷环对BPEB配体的切割归因于DHBDC配体中的两个羟基的氢键。在具有BDC配体的类似金属有机聚合物框架中，聚-BPCB不能解聚。因此，本研究提供了对环丁烷聚合物的可逆切割的一些新见解。基于环丁烷的这些聚合物材料可以是环境良性的，因为这些可以将它们解聚以产生容易的一次性和可降解的单体。

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  • 来源
    《Crystal growth & design》 |2019年第3期|共5页
  • 作者

    Park In-Hyeok; Sasaki Kenta; Quah Hong Sheng; Lee Eunji; Ohba Masaaki; Lee Shim Sung; Vittal Jagadese J.;

  • 作者单位

    Natl Univ Singapore Dept Chem 3 Sci Dr 3 Singapore 117543 Singapore;

    Natl Univ Singapore Dept Chem 3 Sci Dr 3 Singapore 117543 Singapore;

    Natl Univ Singapore Dept Chem 3 Sci Dr 3 Singapore 117543 Singapore;

    Gyeongsang Natl Univ Dept Chem Jinju 52828 South Korea;

    Kyushu Univ Fac Sci Dept Chem Nishi Ku 744 Motooka Fukuoka Fukuoka 8190395 Japan;

    Gyeongsang Natl Univ Dept Chem Jinju 52828 South Korea;

    Natl Univ Singapore Dept Chem 3 Sci Dr 3 Singapore 117543 Singapore;

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