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

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 {Ce11Mo96}. By virtue of the tailor-made open cavity, the {Ce11Mo96} 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. Polyoxometalates (POMs) are molecular clusters with diverse structures. Here authors present the synthesis of POMs by Ce-mediated molecular tailoring from gigantic {Mo-132} into half-closed {Ce11Mo96}, with proton conductivity nearly two orders of magnitude higher than {Mo-132}.

Automated summary

In this study, the authors present a method for the precise synthesis of polyoxometalates (POMs) through Ce-mediated molecular tailoring, resulting in the transformation of gigantic {Mo-132} into a half-closed {Ce11Mo96}, which exhibits significantly enhanced proton conductivity compared to {Mo-132}.