Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

Abstract

Supportinginformation (all synthetic methods, NMR and mass spectroscopic analysis, dynamicl ight scattering and cyclic voltammetry experiments) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.

Supramolecular Aggregation Control in Polyoxometalates Covalently Functionalized with Oligoaromatic Groups

“…The organic azide was covalently anchored to the lacunary α 2 ‐Dawson cluster ( n Bu 4 N) 9 K[α 2 ‐P 2 W 17 O 61 ] ( C1 ) [15] by reacting both components (molar ratio 3.3 : 1; azide : cluster) in heated ( T =110 °C) N,N‐dimethyl acetamide solution containing 0.4 M HCl aq for 24 h (Figure 2). After workup (details see Supporting Information), the product, (nBu 4 N) 6 [α 2 ‐P 2 W 17 O 61 (POCH 2 C 6 H 4 N 3 ) 2 ] ( CP1 ) was obtained as a yellow solid in 80 % yield based on ( n Bu 4 N) 9 K[α 2 ‐P 2 W 17 O 61 ] ( C1 ).…”

“…Supramolecular organic‐inorganic hybrid systems hold great promise as the next‐generation of functional materials [1,2] . In molecular metal oxide (polyoxometalate, POM) chemistry, [3,4] the last decade has seen immense progress in the covalent organo‐functionalization of POMs, [5–8] leading to their use in areas ranging from supramolecular chemistry [9–11] and energy conversion/storage [12–14] to electronic nanomaterials [15,16] and covalent POM‐bioconjugates [17,18] . POMs are ideal molecular platforms for (bio‐)organo‐functionalization, as they introduce redox‐, [19] photo‐, [20] catalytic [21] and magnetic activity [22] .…”

The effect of ionic versus covalent functionalization of polyoxometalate hybrid materials with coordinating subunits on their stability and interaction with DNA

“…WD POM hybrids with terpyridine-type ligands are known in the literature from both covalent and ionic approaches. The majority of papers focus on the covalent bonding of terpyridine ligands to WD POM, where organosilyl 51,52 or organophosphonate 53,54 functionalized WD POMs can be postfunctionalized with terpyridine ligand-based complexes. In contrast, a distinct minority can be found in the literature showing ionic bonding between WD POM and terpyridine ligand.…”