A Self-Assembled Trigonal Prismatic Molecular Vessel for Catalytic Dehydration Reactions in Water
A Self-Assembled Trigonal Prismatic Molecular Vessel for Catalytic Dehydration Reactions in Water
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DOI：
10.1002/chem.201702263
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发表时间：
2017-09-12
影响因子：
4.3
通讯作者：
Mukherjee, Partha Sarathi
中科院分区：
文献类型：
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作者：
Das, Paramita;Kumar, Atul;Mukherjee, Partha Sarathi
通过两组分配位驱动Pd-Ⅱ90度受体与四咪唑供体的自组装，合成了一种水溶性Pd-6三棱柱(A)。棱镜的壁是由三个共轭的芳香族积木构成的，这意味着棱镜的受限口袋是疏水的。除了疏水空腔，大的产品出口窗口使A成为理想的分子容器，在其受限的纳米空间中催化水介质中具有挑战性的伪多组分脱水反应。本研究利用超分子容器对反应条件进行微调，尝试选择性地生成中间体四酮和黄原烯。此外，在类似的反应条件下，在没有A的情况下脱水产物的产率很低或没有，这支持了桶的受限空间在水中促进这种反应的能力。此外，我们重点研究了锚定在Pd-II配位结构中的四亚乙基四咪唑单元的木质化；在水存在的情况下实现了反阴离子依赖的聚集诱导发射。
A water-soluble Pd-6 trigonal prism (A) was synthesized by two-component coordination-driven self-assembly of a Pd-II 90 degrees acceptor with a tetraimidazole donor. The walls of the prism are constructed by three conjugated aromatic building blocks, which means that the confined pocket of the prism is hydrophobic. In addition to the hydrophobic cavity, large product egress windows make A an ideal molecular vessel to catalyze otherwise challenging pseudo-multicomponent dehydration reactions in its confined nanospace in aqueous medium. This study is an attempt at selective generation of the intermediate tetraketones and xanthenes by fine-tuning the reaction conditions employing a supramolecular molecular vessel. Moreover, either poor or no yield of the dehydrated products in the absence of A under similar reaction conditions supports the ability of the confined space of the barrel to promote such reactions in water. Furthermore, we focused on the rigidification of the tetraphenylethylene-based tetraimidazole unit anchored within the Pd-II coordination architecture; enabling counter-anion dependent aggregation induced emission in the presence of water.