Qiu Fenglei, Zhang Xinting, Wang Wenjing, Su Kongzhao, Yuan Daqiang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
College of Chemistry, Fuzhou University, Fuzhou 350116, China.
J Am Chem Soc. 2025 Mar 12;147(10):8500-8512. doi: 10.1021/jacs.4c16508. Epub 2025 Mar 2.
The development of new chiral building blocks for constructing complex chiral architectures, such as macrocycles and cages, is both crucial and challenging. Although concave-shaped calixarenes have been established as versatile building blocks for the synthesis of cage compounds, there are no reports on cages constructed from chiral calix[4]arene derivatives. Herein, we present a straightforward and effective method for gram-scale synthesis of a new member of chiral calix[4]arene macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As a proof of concept, we functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via the Duff reaction to construct chiral porous organic cages (CPOCs) using polyamine synthons. Specifically, we employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine and tris(4-aminophenyl)amine, to assemble with PC[4]ACHO enantiomers, resulting in [2 + 4] lantern-shaped and [6 + 8] truncated octahedral CPOCs, respectively. These structures have been unambiguously characterized by single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy. Notably, the [6 + 8] truncated CPOCs exhibit internal diameters of approximately 3.1 nm, a cavity volume of around 5300 Å, and high specific surface areas of up to 1300 m g after desolvation, making them among the largest CPOCs reported. Additionally, investigations into their chiral sensing performance demonstrate that these PC[4]A-based CPOCs enable the enantioselective recognition of amino acids and their derivatives. This work strongly suggests that PC[4]A can serve as an excellent building block for the rational design of chiral materials with practical applications.
开发用于构建复杂手性结构（如大环和笼状结构）的新手性砌块既至关重要又具有挑战性。尽管凹形杯芳烃已被确立为合成笼状化合物的通用砌块，但尚无关于由手性杯[4]芳烃衍生物构建的笼状结构的报道。在此，我们提出了一种直接有效的方法，用于克级规模合成手性杯[4]芳烃大环对映体的一个新成员，即苯酚[4]芳烃（PC[4]A）。作为概念验证，我们通过达夫反应将这些对映体官能化为四甲酰基苯酚[4]芳烃（PC[4]ACHO）衍生物，使用多胺合成子构建手性多孔有机笼（CPOCs）。具体而言，我们使用两种荧光胺合成子，双（4 - 氨基苯基）苯胺和三（4 - 氨基苯基）胺，分别与PC[4]ACHO对映体组装，得到[2 + 4]灯笼形和[6 + 8]截顶八面体形的CPOCs。这些结构已通过单晶X射线衍射和圆二色性（CD）光谱进行了明确表征。值得注意的是，[6 + 8]截顶的CPOCs在去溶剂化后内径约为3.1 nm，空腔体积约为5300 Å，比表面积高达1300 m²/g，使其成为报道的最大CPOCs之一。此外，对其手性传感性能的研究表明，这些基于PC[4]A的CPOCs能够对氨基酸及其衍生物进行对映选择性识别。这项工作有力地表明，PC[4]A可作为合理设计具有实际应用的手性材料的优良砌块。
