Multi-Template-Guided Synthesis of High-Dimensional Molecular Assemblies for Humidity Gradient-Based Power Generators

B Li and XZ Duan and YZ Cui and T Li and XY Chen and QQ Liu and X Liu and YX Meng and WB Ren and LY Wang and S Liang and HY Zang, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 63, e202408096 (2024).

DOI: 10.1002/anie.202408096

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 (TeO3(Mo2O2S2)3O2(OH)(C5O2H7)34- TeMo6) into tetrahedral cages ((TeO3)4(Mo2O2S2)12(OH)12(C9H9O4P)68- Te4Mo24 and (AsO4)4(Mo2O2S2)12(OH)12(C9H9O6)412- As4Mo24), while steric hindrance from anionic templates further assists in assembling cages into an open quadruply twisted M & ouml;bius nanobelt ((C6H5O3P)8(Mo2O2S2)24(OH)24(C8H10O4)1216- P8Mo48). Among these structures, the hydrophilic-hydrophobic hybrid cage Te4Mo24 emerges as an exemplary molecular model for proton conduction and serves as a prototype for humidity gradient-based power generators (HGPGs). The Te4Mo24-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-2 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. Organized assembly of fundamental building blocks into intricate molecular architectures remains challenging due to the dynamic building blocks. A general strategy has been developed to synthesize high-dimensional complex architectures by choosing appropriate anion templates and flexible, non-planar organic linkers. Further, the complex architecture possesses multifunctions suitable for humidity-electric power generation. image

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