Li Bo, Duan Xiaozheng, Cui Yunzuo, Li Teng, Chen Xinyu, Liu Qianqian, Liu Xin, Meng Yuxi, Ren Weibo, Wang Liying, Liang Song, Zang Hong-Ying
Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Universities of Jilin Province Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130022, China.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202408096. doi: 10.1002/anie.202408096. Epub 2024 Sep 13.
Systematically orchestrating fundamental building blocks into intricate high-dimensional molecular assemblies at molecular level is imperative for multifunctionality integration. However, this remains a formidable task in crystal engineering due to the dynamic nature of inorganic building blocks. Herein, we develop a multi-template-guided strategy to control building blocks. The coordination modes of ligands and the spatial hindrance of anionic templates are pivotal in dictating the overall structures. Flexible multi-dentate linkers selectively promote the formation of oligomeric assembly ([TeO(MoOS)O(OH)(COH)] {TeMo}) into tetrahedral cages ([(TeO)(MoOS)(OH)(CHOP)] {TeMo} and [(AsO)(MoOS)(OH)(CHO)] {AsMo}), while steric hindrance from anionic templates further assists in assembling cages into an open quadruply twisted Möbius nanobelt ([(CHOP)(MoOS)(OH)(CHO)] {PMo}). Among these structures, the hydrophilic-hydrophobic hybrid cage {TeMo} emerges as an exemplary molecular model for proton conduction and serves as a prototype for humidity gradient-based power generators (HGPGs). The TeMo-PVDF-based HGPG (PVDF=Poly(vinylidene fluoride)) exhibits notable stability and power generation, yielding an open-circuit voltage of 0.51 V and a current density of 77.8 nA cm at room temperature and 90 % relative humidity (RH). Further insights into the interactions between water molecules and microscale molecules within the generator are achieved through molecular dynamics simulations. This endeavor unveils a universal strategy for synthesizing multifunctional integration molecules.
在分子水平上系统地将基本构建块编排成复杂的高维分子组件对于多功能集成至关重要。然而，由于无机构建块的动态性质，这在晶体工程中仍然是一项艰巨的任务。在此，我们开发了一种多模板引导策略来控制构建块。配体的配位模式和阴离子模板的空间位阻在决定整体结构方面起着关键作用。柔性多齿连接体选择性地促进低聚物组装体（[TeO(MoOS)O(OH)(COH)] {TeMo}）形成四面体笼（[(TeO)(MoOS)(OH)(CHOP)] {TeMo}和[(AsO)(MoOS)(OH)(CHO)] {AsMo}），而阴离子模板的空间位阻进一步有助于将笼组装成开放的四重扭曲莫比乌斯纳米带（[(CHOP)(MoOS)(OH)(CHO)] {PMo}）。在这些结构中，亲水 - 疏水混合笼{TeMo}成为质子传导的示例性分子模型，并作为基于湿度梯度的发电机（HGPGs）的原型。基于TeMo - PVDF的HGPG（PVDF = 聚偏二氟乙烯）表现出显著的稳定性和发电能力，在室温及90％相对湿度（RH）下产生0.51 V的开路电压和77.8 nA cm的电流密度。通过分子动力学模拟进一步深入了解了发电机内水分子与微观分子之间的相互作用。这项工作揭示了一种合成多功能集成分子的通用策略。
