Discovery of Heteroatom‐“Embedded” Te⊂{W₁₈O₅₄} Nanofunctional Polyoxometalates by Use of Cryospray Mass Spectrometry

Abstract

Das Cryo‐Spiel: Die hier beschriebenen nanofunktionellen Cluster mit eingebettetem Heteroatom enthalten eine [TeVIO6]6−‐Spezies in einem {W18O54}‐Käfig. Die tellurhaltige Spezies aktiviert nicht nur die {W18O54}‐Clusteroberfläche für die Bildung größerer nanoskaliger Strukturen wie [H10TeVI2W58O198]26−, sondern sie geht auch im Innern des Clusters eine Redoxreaktion von [TeVIO6]6− zu [TeIVO3]2− ein.

Polyoxometallate als Bausteine für funktionelle Nanosysteme

“…Kürzlich haben wir Cluster mit CSI-MS analysiert, um zu sehen, ob Tellurat-Ionen in einen Dawson-Cluster eingeschlossen werden können, und um die Reduktion von Te VI zu Te IV in situ zu verfolgen. [25] Bei diesem neuen Ansatz zur Suche nach Clustern mit eingeschlossenen Templaten wird die Reaktionslösung direkt mit Kryospray-Massenspektrometrie untersucht, was den Analysevorgang deutlich beschleunigt (Abbildung 14).…”

Assemblies based on the directing effect of non-classical W18 anionic clusters and the rod-like trans-1,2-di-(4-pyridyl)-ethylen (bpe)

“…In this field, the non-classical polyanions are not paid equivalent attention and still underdeveloped, presumably due to the reasons of the size, charge, and chemical stability [8]. Among them, the {M 18 } (M¼Mo or W) cluster cage has many versatile features, such as electronic configurability or use as a synthetic platform, which should allow the design of novel functional nano-objects [9]. Usually, these non-classical polyoxoanions have higher negative charges than classical Keggin and Dawson polyoxoanions [10], they need more organic cations for the balance and may emerge novel structure features [11].…”

Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} Polyoxometalates under Supramolecular Control

“…The reaction is based upon the self-organization of two {Te 3 W 38 } units around a single chloride template and the formation of a {Ag 12 } cluster, giving a {Ag 12 }-in-{W 76 } clusterin-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. [6] In this way, it is possible to generate a diverse library of nucleophilic POM "secondary building units" (SBUs) which can serve as well-defined precursors in the formation of larger assemblies, which can be intricately controlled by the use of the heteroanion as well as linking coordinating cations. [1] POMs occupy a unique mesoscopic space between molecular oxo anions and infinite oxides, and offer unique possibilities for materials design at the nanoscale.…”

“…[1] POMs occupy a unique mesoscopic space between molecular oxo anions and infinite oxides, and offer unique possibilities for materials design at the nanoscale. [6] In this way, it is possible to generate a diverse library of nucleophilic POM "secondary building units" (SBUs) which can serve as well-defined precursors in the formation of larger assemblies, which can be intricately controlled by the use of the heteroanion as well as linking coordinating cations. In particular, we have been using anions such as (SeO 3 ) 2À and (TeO 3 ) 2À , which can exert a powerful structure-directing effect as a result of the lone pair of the heteroanion, [5] itself templating massive structures.…”

“…[2][3][4] In polyoxotungstates, architectural control can be achieved at the fragment level by carefully selecting the heteroanion templates. [6] In this way, it is possible to generate a diverse library of nucleophilic POM "secondary building units" (SBUs) which can serve as well-defined precursors in the formation of larger assemblies, which can be intricately controlled by the use of the heteroanion as well as linking coordinating cations. [6] In this way, it is possible to generate a diverse library of nucleophilic POM "secondary building units" (SBUs) which can serve as well-defined precursors in the formation of larger assemblies, which can be intricately controlled by the use of the heteroanion as well as linking coordinating cations.…”