Assembly of Modular Asymmetric Organic−Inorganic Polyoxometalate Hybrids into Anisotropic Nanostructures

Abstract

Three organic-inorganic hybrid Mn-Anderson polyoxometalates (POMs), with both symmetrical and asymmetrical appended groups, have been synthesized, identified using electrospray mass spectrometry, and isolated using an approach that allows the three AA, BB, and AB compounds to be structurally characterized. Investigation of the self-assembly of the hybrids on hydrophilic surfaces reveals the formation of nanofibres with characteristics that reflect the nature of the substitution of the POM yielding a route to the programmed assembly of anisotropic hybrid nanostructures.

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

“…Asymmetric double-sided hybrid organic-inorganic Anderson-Evans POMs have also been obtained [183] via the re-arrangement of octamolybdate (Figure 7, A4), which was initially achieved with tris-NO 2 decorated on one side and tris-CH 3 on the other [184]. The synthesis involves a reaction mixture containing both tris-ligands, which naturally results in a mixture of three different anions; two symmetrical products (Figure 7, A1) of each organic ligand and one asymmetric (Figure 7, A4) product.…”

Synthesis and Characterization of Single‐Side Organically Grafted Anderson‐Type Polyoxometalates

“…Cronin and coworkers have made some modification following their convenient synthetic route and obtained single crystal structures of symmetric and asymmetric Mn-Anderson-type based hybrid clusters by using mixed organic groups with the same molar ratio. [10] Aiming at multielectrochromic and photochromic properties, Pierre et al obtained one or two spiropyran grafted Anderson-type POMs with Mn III as the center atom through the same synthetic procedure. [11] Very recently, a range of improvements for the isolation of asymmetrically grafted organic-inorganic hybrid Mn-Anderson-type POM compounds were summarized and reported.…”

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

“…These features have allowed POMs to find potential applications in diverse fields (e.g., catalysis, magnetism, biomedicine, spintronics, molecular recognition, optics, conductivity, ion exchange) with implications in current issues of interest related to technology, health, energy, and the environment [11,12,13,14,15]. As inorganic components, POMs have, for example, been combined with amphiphilic molecules or cationic surfactants to construct several discrete architectures (micelles, capsules, vesicles, cones), fibers and wires, or highly ordered bidimensional arrays (self-assembled monolayers, Langmuir and Langmuir–Blodgett films, layer-by-layer structures) [16,17,18,19,20,21,22,23]. They have also been incorporated into several types of organic materials, such as carbon nanotubes, graphene, metal–organic frameworks, and polymeric matrices (either by adsorption or co-polymerization when derivatized with suitable functionalities) [24,25,26,27,28,29,30,31,32,33].…”