Department of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 52828, South Korea.
Department of Chemistry, Gangneung-Wonju National University, Gangneung 25457, South Korea.
Inorg Chem. 2021 Apr 19;60(8):5804-5811. doi: 10.1021/acs.inorgchem.1c00114. Epub 2021 Apr 2.
A pillar[5]--trithiacrown (L) capable of metal binding and organic guest threading simultaneously has been employed, and the influence of dinitrile guests [CN(CH)CN ( = 2-6: abbreviated C2-C6)] on the coordination behaviors has been investigated. When the ditopic ligand L was reacted with HgCl in the presence of the C2-C6 guests, the shorter guests C2 and C3 afforded a two-dimensional coordination polymer [HgCl(C2@L)] () and a one-dimensional coordination polymer [(HgCl)(C3@L)] (), respectively. In and , each dinitrile guest threads into the pillararene cavity to form a C2@L or C3@L unit via the host-guest interaction. Further linking of these units by exocyclic Hg-S bonds and anion coordination lead to the formation of coordination products with different dimensionalities. While the use of the longer guests C4-C6 under the same reactions yielded a discrete dimercury(II) complex , [HgCl(CHCN@L)] which contains one acetonitrile solvent molecule because the longer dinitriles do not serve as effective guests. In the NMR and UV-vis studies, the association constants (log ) for the host-guest interactions of L with the dinitrile guests are C2 (4.75) > C3 (4.17) ≫ C4 (2.85) > C5 (2.45) > C6 (too small), indicating that the shorter guests C2 or C3 interact more strongly than longer ones due to the confined interior space of L. Taken collectively, the C2 and C3 guests with proper size-matching promote the formation of coordination polymers and , suggesting that the guest size could be a controlling factor.
一种能够同时进行金属配位和有机客体贯穿的支柱[5]-三噻 Crown（L）已被采用，并研究了二腈客体[CN(CH)CN（=2-6：缩写为 C2-C6）]对配位行为的影响。当双位点配体 L 在存在 C2-C6 客体的情况下与 HgCl 反应时，较短的客体 C2 和 C3 分别提供了二维配位聚合物HgCl(C2@L)和一维配位聚合物(HgCl)(C3@L)。在[]和[]中，每个二腈客体通过主体-客体相互作用贯穿到 Pillararene 腔中，形成 C2@L 或 C3@L 单元。这些单元通过外环 Hg-S 键和阴离子配位的进一步连接导致形成具有不同维度的配位产物。而在相同反应中使用较长的客体 C4-C6 则得到离散的二汞（II）配合物[]，[HgCl(CHCN@L)]，其中含有一个乙腈溶剂分子，因为较长的二腈不能作为有效的客体。在 NMR 和 UV-vis 研究中，L 与二腈客体的主体-客体相互作用的结合常数（log）为 C2（4.75）>C3（4.17）≫C4（2.85）>C5（2.45）>C6（太小），表明由于 L 的受限内部空间，较短的客体 C2 或 C3 比较长的客体相互作用更强。总的来说，具有适当尺寸匹配的 C2 和 C3 客体促进了配位聚合物和[]的形成，这表明客体尺寸可能是一个控制因素。
