A mild post-functionalization method for the vanadium substituted P₂W₁₅V₃ Wells–Dawson polyoxometalate based on a copper catalyzed azide–alkyne cycloaddition

Abstract

A mild post-functionalization method, based on a copper(i) catalyzed azide-alkyne cycloaddition, was developed for the fragile [PWV] (PWV). PWV was functionalized with an azide and used as a platform to attach various alkyne functionalized compounds.

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

“…POMs are molecular metal oxide anions based on early transition metals such as Mo, V, and W. [4] Over recent years, the covalent functionalization of POMs with organic or metal complex groups has led to tremendous progress in functional organic‐inorganic hybrid materials. [ 5 , 6 , 7 , 8 , 9 ] This has led to breakthroughs in bioinorganic hybrids, [10] supramolecular nanostructures[ 11 , 12 , 13 ] and electrochemical surface functionalization. [14] …”

Hexavanadate–Organogold(I) Hybrid Compounds: Synthesis by the Azide–Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution

“…While the usage of azide-terminated POM N requires a Cu­(I) source for the activation of azide–alkyne cycloaddition ( POM N Au ), likewise described for organic analogues, , generation of POM C Au from alkyne-terminated (Scheme ) is due to a self-initiated iClick reaction where Au­(I) acts as the reaction activator. , This is especially an appealing finding for POMs − in view of the emerging iClick − chemistry with metal complexes armed by the corresponding synthons.…”

A Bis-organosilyl-Functionalized Wells–Dawson Polyoxometalate as a Platform for Facile Amine Postfunctionalization

“…Subsequently, the use of 2 as a postfunctionalization platform was examined by reacting it with the nucleophilic benzylamine and Na 2 CO 3 as a base in an acetonitrile solution at 55 °C. The successful use of Na 2 CO 3 has been demonstrated previously, where its insolubility in acetonitrile proved to be ideal for maintaining the POM scaffold, which is sensitive to alkaline environments. However, after overnight reaction and the following workup procedure, the 1 H and 31 P NMR spectra indicated only the presence of the pure starting product.…”

“…However, the synthetic pathway for obtaining the bis-substituted WD POMs that are suitable for the reaction with amine ligands under mild conditions has been not described so far. Inspired by the previous successful use of a nucleophilic substitution reaction for the grafting of organic compounds to a chloride-functionalized Anderson–Evans-type POM and Cu­(I)-catalyzed reactions of azide-functionalized Anderson–Evans-type and WD-type POMs, we envisioned a similar method for the functionalization of the double organosilyl-functionalized [α 2 -P 2 W 17 O 61 ] 10– WD POM. In this work, we describe the synthesis of a hybrid monolacunary WD POM and its postfunctionalization with primary and secondary amines in a reaction that takes place at an electrophilic sp 3 -hybridized carbon localized on the hybrid POM.…”