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

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.