Ce-mediated molecular tailoring on gigantic polyoxometalate {Mo132} into half-closed {Ce11Mo96} for high proton conduction

作者：Xuexin Li, Caihong Li, Ming-Jun Hou, Bo Zhu, Wei‐Chao Chen, Chunyi Sun, Ye Yuan, Wei Guan, Chao Qin, Kui‐Zhan Shao, Xinlong Wang, Zhong‐Min Su · 发表于：Nature Communications · 年份：2023 · DOI：10.1038/s41467-023-40685-0 · 被引用次数：92 · 研究领域：Polyoxometalates: Synthesis and Applications、Metal-Organic Frameworks: Synthesis and Applications、Nanocluster Synthesis and Applications

Abstract Precise synthesis of polyoxometalates (POMs) is important for the fundamental understanding of the relationship between the structure and function of each building motif. However, it is a great challenge to realize the atomic-level tailoring of specific sites in POMs without altering the major framework. Herein, we report the case of Ce-mediated molecular tailoring on gigantic {Mo 132 }, which has a closed structural motif involving a never seen {Mo 110 } decamer. Such capped wheel {Mo 132 } undergoes a quasi-isomerism with known {Mo 132 } ball displaying different optical behaviors. Experiencing an ‘Inner-On-Outer’ binding process with the substituent of {Mo 2 } reactive sites in {Mo 132 }, the site-specific Ce ions drive the dissociation of {Mo 2 * } clipping sites and finally give rise to a predictable half-closed product {Ce 11 Mo 96 }. By virtue of the tailor-made open cavity, the {Ce 11 Mo 96 } achieves high proton conduction, nearly two orders of magnitude than that of {Mo 132 }. This work offers a significant step toward the controllable assembly of POM clusters through a Ce-mediated molecular tailoring process for desirable properties.