Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates. Issue 13 (6th March 2023)

• Record Type: Journal Article
• Authors: Repp, Stefan; Junginger, Kim Lara; Sorsche, Dieter; Zorn, Theresa; Pöppler, Ann-Christin; Kikukawa, Yuji; Hayashi, Yoshihito; Streb, Carsten
• Is Part Of: Dalton transactions. Volume 52:Issue 13(2023)
• Page Start: 4002
• Page End: 4007
• Publication Date: 2023-03-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d3dt00252g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Insights into the template-induced self-assembly of dodecanuclear polyoxovanadate host–guest complexes is provided by solution and solid-state methods. 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, [V12 O32 X] n − (X = Cl −, Br −, NO3 − ). A combination of crystallographic analyses, spectroscopic studies and in situ as well as solid-state 51 V 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.