Issue 13, 2023

Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates

Abstract

The self-assembly of molecular metal oxides, polyoxometalates (POMs), can be controlled using internal or, more rarely, external templates. Here, we explore how the interplay between internal templates (halides, oxoanions) and organic external templates (protonated cyclene species) affect the self-assembly of a model polyoxovanadate cluster, [V12O32X]n (X = Cl, Br, NO3). A combination of crystallographic analyses, spectroscopic studies and in situ as well as solid-state 51V NMR spectroscopy provide critical insights into the initial formation of an intermediate vanadate species formed during the process. Structural and spectroscopic studies suggest that a direct interaction between internal and external templates allows tuning of the internal template position within the cluster cavity. These insights form the basis for further developing the template-driven synthetic chemistry of polyoxovanadates.

Graphical abstract: Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates

Supplementary files

Article information

Article type
Paper
Submitted
26 jan 2023
Accepted
22 feb 2023
First published
23 feb 2023

Dalton Trans., 2023,52, 4002-4007

Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates

S. Repp, K. L. Junginger, D. Sorsche, T. Zorn, A. Pöppler, Y. Kikukawa, Y. Hayashi and C. Streb, Dalton Trans., 2023, 52, 4002 DOI: 10.1039/D3DT00252G

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