Tan Liangxiao, Zheng Kaikai, Zhou Jun-Hao, Cao Wei, Zhang Peng, Cao Xingzhong, Yuan Jiayin, Sun Jian-Ke
MOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology (Zhuhai), Beijing Institute of Technology, Beijing, PR China.
College of Chemical and Biological Engineering, Zhejiang University, Zhejiang, PR China.
Nat Commun. 2025 Aug 28;16(1):8033. doi: 10.1038/s41467-025-63126-6.
The direct liquefaction of molecular cages by incorporating alkyl chains as sterically hindered fluids, without compromising porosity due to self-filling, presents a significant challenge. Here, we demonstrate that transforming hydrophobic amine cages into hydrophilic ammonium cages via quaternization with poly(ethylene glycol) bearing a terminal carboxylic acid produces a series of targeted type I porous liquid molecules featuring a porous ammonium cage as the cation and multiple carboxylate ions as anions on a kilogram scale. The hydrophobic-hydrophilic incompatibility between the cation and anion prevents alkyl chain interpenetration, preserving porosity and liquidity. Notably, photoirradiation induces stable radical generation (lasting over a year) and a red-shift in absorption toward the near-infrared region for photothermal conversion-an unexpected phenomenon in porous liquids. Utilizing this unique property, we further enhance solvent-free photothermal catalytic performance by encapsulating Au clusters within the cage cavities. This study provides new insights into the straightforward synthesis of porous liquids, akin to conventional chemical synthesis of targeted molecules through precise precursor stoichiometry. It also facilitates the extension of their functions and applications from traditional sorption to smart photothermal conversion/catalysis, promising significant advancements in these fields.
通过引入烷基链作为空间位阻流体来实现分子笼的直接液化，同时又不因自填充而损害孔隙率，这是一项重大挑战。在此，我们证明，通过用带有末端羧酸的聚乙二醇进行季铵化反应，将疏水性胺笼转变为亲水性铵笼，可在千克规模上制备出一系列目标I型多孔液体分子，其特征是以多孔铵笼为阳离子，多个羧酸根离子为阴离子。阳离子和阴离子之间的疏水 - 亲水性不相容性可防止烷基链相互渗透，从而保持孔隙率和流动性。值得注意的是，光照射会诱导稳定的自由基生成（持续一年以上），并且吸收光谱向近红外区域发生红移以进行光热转换——这在多孔液体中是一种意想不到的现象。利用这一独特性质，我们通过将金簇封装在笼腔内进一步提高了无溶剂光热催化性能。这项研究为多孔液体的直接合成提供了新的见解，类似于通过精确的前体化学计量比进行传统的目标分子化学合成。它还促进了其功能和应用从传统吸附扩展到智能光热转换/催化，有望在这些领域取得重大进展。
