Molecular Design of Electron‐Rich Polyoxometalates Based Clusters Enabling Intelligent Energy Storage

The fabrication of molecular cluster‐based intelligent energy storage systems remains a significant challenge due to the intricacies of multifunctional integration at the molecular level. In this work, low‐valent metal atoms are successfully encapsulated within ɛ ‐type Keggin structures, yielding a novel cluster denoted as CuMo 16 . This unique structure displayed the characteristic “molybdenum red” coloration, with a high degree of reduction (76.47%), which played a pivotal role in enhancing its electrochemical properties. The specialized configuration significantly enhanced multi‐proton‐coupled electron transfer kinetics, enabling efficient and rapid electron storage and release, with up to thirteen electrons per molecule. To construct an intelligent energy storage device, CuMo 16 is employed as a proton‐coupled electron‐active material and embedded within a polyvinyl alcohol (PVA) matrix, resulting in the flexible, wearable, rechargeable devices. The flexible electronics not only demonstrate real‐time human motion detection but also exhibit remarkable energy storage performance, reaching a peak capacity of 194.19 mAh g −1 and maintaining 68.2% capacity retention after 2500 cycles. Molecular dynamics simulations reveal that integrating CuMo 16 significantly enhances the intelligent storage performance of flexible electronics, and molecular regulation of CuMo 16 content provides an effective strategy for optimizing flexible electronic devices. This study lays the foundation for the development of cluster‐based intelligent energy storage systems.