Anna Proust

Sorbonne Université | UPMC · Institut Parisien de Chimie Moléculaire (IPCM)

In this work, Preyssler‐type POM (NH4)14[NaP5W30O110].44H2O (NH4P5W30), has been synthesised and its electrochemical behaviour in solution was examined at the surface of glassy carbon (GC) and gold electrodes. Furthermore, multilayer assemblies of NH4P5W30 POM were constructed onto the surfaces of GCE, gold electrode, and gold quartz electrode via...

We study the low-frequency noise (LFN), i.e. flicker noise, also referred to as 1/f noise, in 2D networks of molecularly functionalized gold nanoparticles (NMN: nanoparticle-molecule network). We examine the noise behaviors of the NMN hosting alkyl chains (octanethiol), fatty acid oleic acids (oleylamine), redox molecule switches (polyoxometalate d...

Quaternary ammonium salts of metal derivatives of polyoxometalates [XW11O39M(H2O)]n- (X = P, Si; M = Cr, Mn, Co, Ni, Zn) were successfully tested instead of quaternary ammonium halides as catalysts...

A few nanometers thick film of polyoxometalates has been covalently assembled onto ITO for resistive switching.

We demonstrate a high electron conductivity (>102 S/cm and up to 103 S/cm) of tungsten suboxide W18O52.4−52.9 (or equivalently WO2.91−2.94) nanotubes (2–3 nm in diameter, ∼μm long). The conductivity is measured in the temperature range of 120–300 K by a four-probe scanning tunneling microscope in ultrahigh vacuum. The nanotubes are synthesized by a...

We demonstrate a high electron conductivity (> 10^2 S/cm and up to 10^3 S/cm) of tungsten suboxide W18O(52.4-52.9)(or equivalently WO(2.91-2.94)) nanotubes (2 to 3 nm in diameter, ca. micrometer long). The conductivity is measured in the temperature range 120 to 300K by a four probe scanning tunneling microscope in ultra high vacuum. The nanotubes...

Clusters and oxo-clusters are drawing attention for their amazing physical properties, especially at the scale of the single molecule. However, chemical methods to organize them on a surface in such...

Polyoxometalates are nanoscale molecular oxides with promising properties that are currently explored for molecule-based memory devices. In this work, we synthesize a series of Preyssler polyoxometalates (POMs), [Na⊂P5W30O110]14-, stabilized with four different counterions, H+, K+, NH4+, and tetrabutylammonium (TBA+). We study the electron transpor...

This article describes the synthesis and characterization of an organic-inorganic hybrid polyoxometalate functionalized by a short link with a tripodal N-based ligand and its copper complex. Upon visible light irradiation, the latter is able to store up to three reducing equivalents. The locus of the reduction is discussed based on physicochemical...

Polyoxometalates are nanoscale molecular oxides with promising properties that are currently explored for molecule-based memory devices. In this work, we synthesize a series of Preyssler polyoxometalates (POMs), (Na-P5W30O110)14-,stabilized with four different counterions, H+, K+, NH4+ and tetrabutylammonium (TBA+), and we study the electron transp...

Correction for ‘Redox-controlled conductance of polyoxometalate molecular junctions’ by Cécile Huez et al. , Nanoscale , 2022, 14 , 13790–13800, https://doi.org/10.1039/D2NR03457C.

We demonstrate the reversible in situ photoreduction of molecular junctions of phosphomolybdate [PMo12O40]3- monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4- molecular junction is increased by ca. 10, this open-shell state is stab...

Drift tube ion mobility spectrometry (DTIMS) coupled with mass spectrometry was used to determine the collision cross-sections (DTCCS) of polyoxometalate anions in helium and nitrogen. As the geometry of the ion, more than its mass, determines the collision cross-section with a given drift gas molecule, we found that both Lindqvist ions Mo6O192- an...

The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9M...

NiII and MnIII Schiff base complexes (Salophen‐Ni and Salophen‐MnCl) bearing a pending carboxylic group were prepared and characterized. Both complexes were grafted onto a mesoporous amino‐functionalized SBA‐15 silica, by formation of an amide function between the propylamine groups of the support and the carboxylic acid functions of the salophen l...

The synthesis of the first mesogenic donor‐acceptor polyoxometalate (POM)‐based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small‐ and wide‐angle X‐ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves...

The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron‐dipyrromethene) light‐harvesting units were examined. Evaluated here in this polyanionic donor‐acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The...

Four hybrid polyoxometalate–porphyrin copolymer films were obtained by the electrooxidation of zinc-β-octaethylporphyrin (ZnOEP) or 5,15-ditolylporphyrin (H2T2P) in the presence of organosilyl functionalized Keggin-type POMs TBA3[PW11Si2O40C26H16N2] (abbreviated Py-PW11Si2-Py) and Dawson-type POMs TBA6[P2W17Si2O62C26H16N2] (abbreviated Py-P2W17Si2-...

Titanium complexes of silanol functionalized polyoxometalates (THA)3[SbW9O33(RSiO)3Ti(OⁱPr)] (Ti‐SiloxPOMs) catalyze alkene oxidation with tert‐butyl hydrogen peroxide (TBHP). However catalytic activity and product distribution in the oxidation of allylic alcohols are shown to depend on the steric surrounding generated by the SiloxPOM (R=tBu, ⁱPr,...

H+ modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described. The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates (POMs, where KM = [PM11O39] and M = Mo or W) covalently grafted via an organotin linker to bodipy (BOD) photosensitizers. The relative potentials of...

Identifying descriptors that govern charge transport in molecular electronics is of prime importance for the elaboration of devices. The effects of molecule characteristics, such as size, bulkiness or charge, have been widely reported. Herein, we show that the molecule polarizability can be a crucial parameter to consider. To this end, platinum nan...

The synthesis of the first mesogenic donor‐acceptor polyoxometalate (POM)‐based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small‐ and wide‐angle X‐ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves...

The optical and electrochemical properties of a series of polyoxometalates (POMs) oxoclusters decorated with two bodipy (boron-dipyrromethene) light harvesting units were examined. We evaluated in this polyanionic donor-acceptor system the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. Our res...

Immobilization of polyoxometalates (POMs) onto oxides is relevant to many applications in the fields of catalysis, energy conversion/storage or molecular electronics. Optimization and understanding the molecule/oxide interface is crucial to rationally improve the performance of the final molecular materials. We herein describe the synthesis and cov...

Immobilization of polyoxometalates (POMs) onto oxides is relevant to many applications in the fields of catalysis, energy conversion/storage or molecular electronics. Optimization and understanding the molecule/oxide interface is crucial to rationally improve the performance of the final molecular materials. We herein describe the synthesis and cov...

The formation of hierarchical nanostructures using preformed dumbbell-like species made of covalent organic–inorganic polyoxometalate (POM)-based hybrids is herein described. In this system, the presence of charged subunits (POM, metal linkers, and counter ions) in the complex molecular architecture can drive their aggregation, which results from a...

Organic solar cells, characterized by a symmetrical regular layered structure, are very promising systems for developing green, low cost, and flexible solar energy conversion devices. Despite the efficiencies being appealing (over 17%), the technological transfer is still limited by the low durability. Several processes, in bulk and at interface, a...

Guest Editors Anna Proust and Rinaldo Poli briefly present the Division of Coordination Chemistry of the French Chemical Society and the annual prize it awards to selected scientists, who are the authors of this Society Prizewinner Collection. image John Wiley & Sons, Ltd.

The power of Fourier transformed large amplitude alternating current voltammetry (FTACV) has been applied to parameterise the reduction of the phospho-tungstate [PW11O39{Sn(C6H4)C≡C(C6H4)(N3C4H10)}]4- polyoxometalate (KWSn[N3C4H10]4-/5-/6- processes) at glassy carbon (GC), gold (Au) and platinum (Pt) electrodes as well as its GC surface confined KW...

The Front Cover shows the oxidation of limonene to epoxylimonene with, in the background, orange trees typical of Réunion Island, where some of the studies reported in this manuscript have been carried out. Terpenes, especially limonene, are particularly present in citrus fruits, which constitute a part of the island's natural resources. The use of...

This class of catalysts may thus be considered as ideal candidates for the scale‐up of the selective oxidation of terpenes to a practical biorefinery, that is, a facility that processes agricultural material to commercially useful chemicals … Read more about the story behind the cover in the Cover Profile and about the research itself in the Full P...

The epoxidation of allylic alcohols with H2O2 catalyzed by the hybrid [α-B-SbW9O33(tBuSiO)3Ti(OiPr)]3- (1) anion as molec-ular model of heterogeneous Ti-silicalite TS-1 catalyst was analyzed by means of DFT to determine the main factors that control the catalytic process and, finally, to improve the value of the available catalysts. Our calculation...

The design and synthesis of a supramolecular square composed of polyoxometalate-based hybrid donors and ethylenediamine palladium(II) nodes are reported. The structure of the metallomacrocycle scaffold was inferred by diffusion NMR, small-angle X-ray scattering (SAXS), and molecular modeling. The metallomacrocycle scaffold that contains negatively...

The amplification effect of polyoxometalates (POMs) on the efficiency of dye-sensitized nano-ITO cathodes is disclosed. The use of hybrid polyoxometalates of the type [PW11O39{SnC6H4-≡-C6H4F}]4-, F standing for a carboxylic group (POM-COOH) or a diazonium unit, allows to control the loading of the POMs on the electrode and to investigate key parame...

The catalytic performances of three organophosphonyl/arsonyl derivatives of POMs were evaluated for the epoxidation of limonene in acetonitrile, using aqueous H2O2 as the oxidant. All three W‐based POMs catalysts operated without any additional transition‐metal ions and displayed excellent conversion for limonene at temperatures varying from 4 to 5...

The binary assembly DDA-{Mo132}/OA-γ-Fe2O3 (DDA = didodecyldimethylammonium, {Mo132} = [Mo132O372(CH3COO)30(H2O)72]⁴²⁻, OA = oleic acid) constitutes one of the two examples in the literature of binary superlattices made of a mixing of nanocrystals and oxo-clusters. In a precedent work, we reported in details the preparation of such magnetic binary...

. In this work, mesoporous materials based on inorganic/organic polyoxometalate (POM) hybrids with the ability of further incorporating heterometallic lanthanum cations were designed. On the basis of the La3+ coordination to vacant organophosphonyle derivatives of POMs previously studied, herein POMs-grafted onto an amino-functionalized mesoporous...

Nanocrystals are often described as interesting materials for the design of low-cost optoelectronic devices especially in the infrared range. However the driving materials reaching infrared absorption are generally heavy metal-containing (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped sem...

Polyoxometalates (POMs) are redox-active molecular oxides, which attract growing interest for their integration into nano-devices, such as high-density data storage non-volatile memories. In this work, we investigated the electrostatic deposition of the negatively charged [H7P8W48O184]³³⁻- POM onto positively charged 8-amino-1-octanethiol self-asse...

We report a study of alpha-[P2W18O62]6-, Wells-Dawson polyoxometalate layers deposited on ITO coated glass substrates. A variety of techniques has been used including atomic force microscopy for surface topography characterization, current mapping and current-voltage characteristics, X-ray photoemission spectroscopy for chemical analysis, UV-visibl...

Nanocrystals are often described as an interesting strategy for the design of low-cost optoelectronic devices especially in the infrared range. However the driving materials reaching infrared absorption are generally heavy metalcontaining (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped se...

The hybrid derivative of heteropolytungstate bearing two aniline groups, namely (ⁿBu4N)3[NaHPW9O34{As(O)C6H4NH2}2], was post-functionalized in the presence of 1,4-phenylene diisothiocyanate (PDITC). The resulting molecular moiety was characterized by IR, ¹H and ³¹P NMR spectroscopy. In a second step, this post-functionalized hybrid of polyoxometala...

Intraband and plasmonic transitions have appeared over the last years as an interesting tool to achieve optical absorption in the mid infrared. Tuning the doping magnitude has become a major challenge not only to tune the optical spectrum but also properties such as the dark current or the time response. Here we investigate the case of self-doped H...

Here we report on the use of a silanol-decorated polyoxotungstate, [SbW9O33(tBuSiOH)3]3− (1), as a molecular support to describe the coordination of a vanadium atom at a single-site on silica surfaces. By reacting [V(Mes)3·thf] (Mes= 2,4,6-trimethylphenyl) with 1 in tetrahydrofuran, the vanadium(III) derivative [SbW9O33(tBuSiO)3V(thf)]3− (2) was ob...

Polyoxometalates (POMs) are unconventional electro-active molecules with a great potential for applications in molecular memories, providing efficient processing steps onto electrodes are available. The synthesis of the organic-inorganic polyoxometalate hybrids [PM11O39{Sn(C6H4)C≡C(C6H4)N2}]3- (M = Mo, W) endowed with a remote diazonium function is...

Significance Hierarchical self-assembly is a powerful route allowing the elaboration of complex supramolecular architectures with emergent structuration or properties. Starting from well-defined molecular building units, this synthetic strategy relies on the construction of a preassembled structural motif that can further self-assemble through addi...

Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high...

RATIONALE Polyoxometalates (POM) are remarkable oxo‐clusters forming compact highly charged anions. We measured their collision cross sections (CCS) in N2 with drift tube ion mobility spectrometry (DTIMS). These values were then used to calibrate a traveling wave ion mobility spectrometry (TWIMS) device and the accuracy of the calibration was teste...

Controlled design of photoactive hybrids would provide highly active materials for solar energy conversion and photo(electro)catalysis. We describe the kinetics of photoinduced electron transfer in a series of photoactive hybrids based on Keggin-type polyoxometalates (POMs) covalently grafted to bodipy photosensitizers. We show how the electronic p...

Herein, we report on the study of supramolecular assemblies based on polyoxometalates (POMs) upon their modification with amino acids. Two POM-amino acid hybrids were synthesized by coupling a functionalized Keggin type polyoxoanion [PW11O39{Sn(C6H4)C C(C6H4)COOH}]4- with carboxyl-protected (methyl-ester) phenylalanine or diphenylalanine peptides....

We report on a site–isolated model for Ti(IV) by reacting [Ti(iPrO)4] with the silanol–functionalized polyoxotungstates [XW9O34-x(tBuSiOH)3]3- (X= P, x=0, 1; X= Sb, x=1, 2) in tetrahydrofuran. The resulting titanium(IV) complexes [XW9O34-x(tBuSiO)3Ti(OiPr)]3- (X= P, 3; X= Sb, 4) were obtained in monomeric forms both in solution and in the solid sta...

We propose a simple experimental procedure based on the cloud point measurement of a non-ionic surfactant as a tool for (i) esti-mating the super-chaotropic behaviour of polyoxometalates (POMs) and for...

Amino-functionalized core-shell magnetic nanoparticles have been covalently grafted with Polyoxometa-lates (POMs). These multifunctional nanocomposites have been obtained through the coupling of heteropoly-tungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core-shell nanoparticles. The physical pr...

The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different fro...

The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (λem (closed form)=530 nm, λem (open form)=670 nm) and that the fluorescence of the BSPR unit of the hybrid...

The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (λem (closed form)=530 nm, λem (open form)=670 nm) and that the fluorescence of the BSPR unit of the hybrid...

Polyoxometalate (POM) chemistry has recently offered excellent examples of single ion magnets (SIMs) and molecular spin qubits. Compared with conventional coordination compounds, POMs provide rigid and highly symmetric coordination sites. However, all POM-based SIMs reported to date exhibit a very limited range of possibilities for chemical process...

Post-functionalization of organically modified polyoxometalates (POMs) is a powerful synthetic tool to devise functional building blocks for the rational elaboration of POM-based molecular materials. In this personal account we focus on iodoaryl-terminated POM platforms, describe reliable routes to the synthesis of covalent organic-inorganic POM-ba...

The polyoxomolybdate hybrid TBA3[PMo11O39{Sn(C6H4)C≡C(C6H4)N2}] K(Mo)Sn[N2(+)] was prepared through Sonogashira-type coupling between TBA4[PMo11O39{Sn(C6H4)I}] K(Mo)Sn[I] and an excess of 3,3-diethyl-1-(4-ethynylphenyl)triaz-1-ene bearing a protected diazonium function, followed by its deprotection by the addition of trifluoroacetic acid (TFA). Thi...

The interfacing of polyoxometalates and graphene can be considered as an innovative way to generate hybrid structures that take advantage of the properties of both components. Polyoxometalates are redox and photo sensitive compounds with high temperature stability (up to 400 °C for some) showing tunable properties depending on the metal incorporate...

The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In a strongly dissociating solvent, a discrete metallomacrocycle, described as a molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scatter...

A 2D supramolecular honeycomb network built on hydrogen bonding of Perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (Melamine) has been self-assembled on Au(111) by a solution processed method. The ability of the porous network to host functional molecular oxides or polyoxometalates (POMs) has been investigat...

In the present article, the successful coassembly of spherical 6.2 nm-maghemite (g-Fe2O3) nanocrystals and giant polyoxometalates (POMs) such as 2.9 nm-{Mo132} is demonstrated. To do so, colloidal solutions of oleic acid-capped g-Fe2O3 and long chain alkylammonium-encapsulated {Mo132} dispersed in chloroform are mixed together and supported self-or...

A polyoxometalate-based molecular triangle has been synthesized through the metal-driven self-assembly of covalent organic/inorganic hybrid oxo-clusters with remote pyridyl binding sites. The new metallomacrocycle was unambiguously characterized by using a combination of (1) H NMR spectroscopy, 2D diffusion NMR spectroscopy (DOSY), electrospray ion...

In the present article, the successful coassembly of spherical 6.2 nm maghemite (γ-Fe2 O3 ) nanocrystals and giant polyoxometalates (POMs) such as 2.9 nm {Mo132 } is demonstrated. To do so, colloidal solutions of oleic acid-capped γ-Fe2 O3 and long-chain alkylammonium-encapsulated {Mo132 } dispersed in chloroform are mixed together and supported se...

The metalation of two different types of silanol-decorated polyoxotungstates, [XW9O34-x(tBuSiOH)3]3- (X = P, x = 0; X = Sb, x = 1) and [PW10O36(tBuSiOH)2]3-, by Cl3VO or (iPrO)3VO has been achieved. The characterization of the resulting oxidovanadium(V) complexes [XW9O34-x(tBuSiO)3VO]3- (X = P, 3; X = Sb, 3′) and [PW10O36(tBuSiO)2VO(iPrO)]3- (4) ha...

Polyoxometalate (POM) hybrids have been covalently immobilized through the formation of amide bonds on several types of mesoporous silica. This work allows the comparison of three POM-based mesoporous systems, obtained with three different silica supports in which either the organic functions of the support (amine vs carboxylic acid) and/or the str...

We report here on the multiproton-multielectron electrochemical reduction of CO2 in homogeneous solution by using (TOA)6[α-SiW11O39Co(_)] (TOA = tetraoctyl ammonium; _ = vacant position in the coordination sphere of Co) as an electrocatalyst. First, the electrochemical behavior of (TOA)6[α-SiW11O39Co(_)] was analyzed in detail by cyclic voltammetry...

As electroactive molecules, polyoxometalates (POMs) have potential in charge trapping or resistive molecular memories, yet scarcely investigated until very recently. Since charge/discharge processes as well as transport properties are dependent upon the organization of the thin layers, we chose to explore a covalent approach and we prepared a diazo...

We easily produced a series or polyoxometalate (POM) nanoparticles by taking benefit from electrostatic attractions between various POMs and alkylammonium cations. These self-assembled supramolecular nanoparticles are fully characterized in terms of shape, nanostructure and physicochemical properties. The nanoparticles differences are discussed on...

We report the design of a polyoxometalate-nanostructured immunosensor for benzo[a]pyrene (B[a]P) detection. The organic-inorganic hybrid polyoxometalate (POM) (NBu4)3[PW11O39{(SiC6H4NH2)2O}] carrying two amine functions was covalently attached to a functionalized gold substrate to achieve a nanometric organization of amine groups at its surface. Py...

In this article the Wells-Dawson polyoxometalate K6[P2W18O62] is grown as an interfacial layer between indium tin oxide and bulk heterojunction of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The structure of the POM layers depends on the thickness and shows a highly anisotropic surface organization. The film...

We demonstrate the success in self-assembling pyrene-modified Dawson–Wells-type polyoxometalates (POMs) with single walled carbon nanotubes (SWCNTs) by means of π–π interactions. In this context, the immobilization of POMs onto SWCNTs is corroborated by aberration-corrected high-resolution electron microscopy, thermogravimetric analysis, and Raman...

A new polyoxomolybdate-based hybrid platform TBA4[PMo11O39{Sn(p-C6H4I)}] is reported. The presence of a post-functionalisable iodo-aryl moiety allows the grafting of a ferrocenyl moiety onto the POM. The electrochemical characterisation shows the effect of molybdenum on the electron reservoir properties of POM-based hybrids, which are further enhan...

Metallic palladium nanoparticles have been generated by hydrogenation with H2 of solutions of several non organometallic PdII-derivatives of heteropolytungstates, at ambient temperature and atmospheric pressure. These nanoparticles have been characterized by various techniques: 31P NMR and Raman spectroscopy, TEM (including cryogenic techniques), D...

Covalent amphiphilic polyoxometalates generated from alkylphosphonic acids have been synthesized, characterized and monitored by multinuclear NMR spectroscopy. Among them, K3H[γ-SiW10O36(C12H25PO)2] has been successfully used as a surfactant for the stabilization of a Winsor I type microemulsion system.

Spontaneously adsorbed monolayers have been formed on gold electrodes using a Keggin polyoxotungstate, with covalently attached alkanethiol linkers of two different lengths. Films of both polyoxotungstates show two well defined reduction processes associated with the polyoxotungstate centers where the ionic liquid, [BMIM][BF4], acts as supporting e...

A Keggin-type POM is attached to gold or glassy carbon surfaces by electro(chemical) or peptidic coupling. In addition to demonstrating the robust attachment of the POMs (by electrochemistry, XPS and IRRAS), the surface concentration, layer thickness and rate constant for electron transfer from the surface to the POMs have been measured. The use of...

The first systems associating in a single molecule polyoxotungstates (POTs) and photochromic organic groups have been elaborated. Using the (TBA)4[PW11O39{Sn(C6H4I)}] precursor, two hybrid organic-inorganic species where a spiropyran derivative (SP) has been covalently grafted onto a {PW11Sn} fragment via a Sonogashira coupling have been successful...

Handy POMs: Several palladium-catalyzed coupling reactions have been applied to polyoxometalate post-functionalization. The feasibility of each reaction with one model substrate was investigated and each set of synthetic conditions was optimized to obtain full conversions and high purity hybrid compounds.

Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provi...

Steady-state irradiation under visible light of a covalent Ir(III)-photosensitized polyoxotungstate is reported. In the presence of a sacrificial electron donor, the photolysis leads to the very efficient photoreduction of the polyoxometalate. Successive formation of the one-electron and two-electron reduced species, which are unambiguously identif...

Compounds [Cr 3III(μ3-O)(O2CPh)5(H2N-sao)(EtOH)2]·EtOH (1·EtOH) and [Cr 3III(μ3-O)(O2CPh)3(H2N-pao)3]NO3·H2N-paoH·EtOH (2·NO3·H2N-paoH·EtOH) have been obtained either in a sequential one-pot, two-step procedure in which Cr(NO3)3·9H2O is first reacted with sodium benzoate in ethanol under reflux, followed by the addition of salicylamidoxime (H2N-sao...

The coordination properties of bisorganophosphonyl and bisorganoarsenyl derivatives of heteropolytungstates towards lanthanides and early-transition-metal cations were studied in organic medium. This new class of vacant polyoxometalate (POM) hybrids proved to conserve coordination sites after the grafting of the {RP=O}2+ or {RAs=O}2+ groups onto th...

Keggin and Dawson-type polyoxometalates (POMs) covalently grafted to heteroleptic cyclometalated iridium(III) complexes (POM–[Ir] dyads) have been prepared by postfunctionalization of organosilyl and organotin POM derivatives. Electronic properties of these 4 photosensitized POM–[Ir] dyads were evaluated by electrochemical measurements and theoreti...

Covalent grafting of heteropolyanions hybrids B,α-[As(III)W(9)O(33){P(O)(CH(2)CH(2)CO(2)H)}(2)](5-) on 3-aminopropyl functionalized SBA-15 has been achieved through the formation of peptide bonds. The covalent link has been confirmed by using IR and (13)C CP MAS NMR spectroscopies. Electrostatic interactions between carboxylate and protonated amine...