Ce-Mediated Molecular Tailoring on an Unprecedented Gigantic Polyoxometalate {Mo132} into Half-Closed Product {Ce11Mo96} for Achieving High Proton Conduction

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 first case of Ce-mediated molecular tailoring on the unprecedented gigantic {Mo132}, which has a closed structural motif involving a never seen {Mo110} decamer. Such capped wheel {Mo132} undergoes a rare quasi-isomerism with known {Mo132} ball displaying different optical behaviors. Experiencing an ‘Inner-On-Outer’ binding process with the substituent of {Mo2} reactive sites in {Mo132}, the site-specific Ce ions drive the dissociation of {Mo2*} clipping sites and finally give rise to a predictable half-closed product {Ce11Mo96}. By virtue of the tailor-made open cavity, the {Ce11Mo96} achieves high proton conduction, nearly two orders of magnitude than that of {Mo132}. This work offers a significant step toward the controllable assembly of POM clusters through a Ce-mediated molecular tailoring process for desirable properties.