Anion-π-Directed Self-Assembly between Di- and Trisulfonates and a Rigid Molecular Cage with Three Electron-Deficient V-Clefts
Anion-π-Directed Self-Assembly between Di- and Trisulfonates and a Rigid Molecular Cage with Three Electron-Deficient V-Clefts
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二磺酸盐和三磺酸盐与具有三个缺电子 V 形裂缝的刚性分子笼之间的阴离子 定向自组装
DOI：
10.1021/acs.inorgchem.9b00295
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发表时间：
2019
影响因子：
4.6
通讯作者：
Wang De-Xian
中科院分区：
文献类型：
--
作者：
Wang Xue-Yuan;Zhu Jun;Wang Qi-Qiang;Ao Yu-Fei;Wang De-Xian
报道了一系列二磺酸和三磺酸阴离子与刚性分子笼之间的阴离子−π自组装。自组装研究建立在X射线结晶学、核磁共振、质谱学和扫描电子显微镜技术相结合的基础上。晶体结构表明，该笼子提供了两个V形缺电子裂隙，通过阴离子−π相互作用来调节磺酸盐基团。根据阴离子的结构不同，这些阴离子表现出不同的分子间相互作用细节，并导致不同的自组装基序的形成。对于1，2-乙二磺酸(EDS2-)、1，3-丙二磺酸(PDS2-)和1，4-丁二磺酸(BDS2-)，形成了非常相似且均匀的二维梯形自组装。具有较长烷基的1，6-己烷二磺酸(HDS2-)形成螺旋链组装，而1，3，5-三(4-磺基苯基)苯(TSPB3-)形成三维骨架结构。在溶液中，核磁共振滴定表明笼子可以络合这些阴离子，结合常数在5-114M-1范围内。在不同浓度和温度下记录的核磁共振谱和电喷雾电离MS进一步证实了自组装的形成。扫描电子显微镜显示了笼子与磺酸盐之间形成的各种自组装的形态。因此，这项研究提供了阴离子−π相互作用在自组装中起决定性作用的证据。
Anion−π-directed self-assembly between a series of di- and trisulfonate anions and a rigid molecular cage1was presented. The self-assembly study was established on a combination of X-ray crystallography, NMR, mass spectrometry (MS), and scanning electron microscopy (SEM) techniques. As revealed in the crystal structures, the cage provided two V-shaped electron-deficient clefts to accommodate sulfonate groups through anion−π interactions. Depending on their structure, the series of anions showed different intermolecular interaction details with the cage and led to the formation of diverse self-assembly motifs. For 1,2-ethanedisulfonate (EDS2–), 1,3-propanedisulfonate (PDS2–), and 1,4-butanedisulfonate (BDS2–), very similar and uniform 2D ladder-like self-assemblies were formed. For 1,6-hexanedisulfonate (HDS2–) with a longer alkyl chain, a helical chain assembly was formed, while 1,3,5-tris(4-sulfophenyl)benzene (TSPB3–) led to a 3D frame structure. In solution, NMR titrations suggested that the cage can complex these anions, with association constants falling in range of 5–114 M–1. NMR spectra recorded at variable concentrations and temperatures and electrospray ionization MS further confirmed self-assembly formation. The morphologies of the diverse self-assemblies formed between the cage and sulfonates were revealed by SEM. This study, hence, provides evidence that anion−π interactions can play decisive roles in self-assembly.