Steady-state irradiation under visible light of a covalent Ir(III)-photosensitized polyoxotungstate is reported. In the presence sacrificial electron donor, photolysis leads to very efficient photoreduction polyoxometalate. Successive formation one-electron and two-electron reduced species, which are unambiguously identified by comparison with spectroelectrochemical measurements, observed significantly faster rate reaction for species. The kinetics photoreduction, correlated reduction...

The metal-driven self-assembly processes of a covalent polyoxometalate (POM)-based hybrid bearing remote terpyridine binding sites have been investigated. In strongly dissociating solvent, discrete metallomacrocycle, described as molecular triangle, is formed and characterized by 2D diffusion NMR spectroscopy (DOSY), small-angle X-ray scattering (SAXS), modeling. less the primary supramolecular structure, combining negatively charged POMs cationic metal linkers, further self-assemble through...

Three new molecular dyads, comprising a bora-3a,4a-diaza-s-indacene (Bodipy) dye linked to two aromatic polycycles via the boron center, have been synthesized and fully characterized. The polycyclic compounds are either pyrene or perylene, mixture of both. Whereas absorption spectral profiles contain important contributions from each subunits, fluorescence occurs exclusively Bodipy fragment. Intramolecular excitation energy transfer is extremely efficient in case, even though overlap...

Keggin and Dawson-type polyoxometalates (POMs) decorated by organometallic [cyclometalated ruthenium(II) polypyridine complex] or organic (pyrene) chromophores were prepared postfunctionalization of hybrid disilylated POM platforms. The connection is made in a very efficient modular way via Sonogashira coupling reactions, which provide rigid linkage between the photoactive centers. Electronic properties have been inferred from electrochemical photophysical studies reflect poor electronic...

Keggin and Dawson-type polyoxometalates (POMs) covalently grafted to heteroleptic cyclometalated iridium(III) complexes (POM–[Ir] dyads) have been prepared by postfunctionalization of organosilyl organotin POM derivatives. Electronic properties these 4 photosensitized POM–[Ir] dyads were evaluated electrochemical measurements theoretical calculations. These studies reveal that the electron acceptor character POMs vary with structural class (Keggin vs. Dawson) chemical anchorage (organosilyl...

Abstract The photophysical properties of a Keggin‐type polyoxometalate (POM) covalently bounded to benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features ( λ em (closed form)=530 nm, (open form)=670 nm) the fluorescence BSPR hybrid is considerably enhanced compared parent compounds. While excitation energy reference compounds (370 close intense absorption responsible photochromic character (350...

The reaction of a cuprous center coordinated to calix[6]arene-based aza-cryptand with dioxygen has been studied. In this system, Cu(I) is bound tren unit that caps the calixarene core at level small rim. As result, although protected from medium by macrocycle, metal presents labile site accessible guest ligands. Indeed, in presence O2, it reacts very fast and irreversible redox process, leading, ultimately, Cu(II) species. coordinating solvent MeCN, one electron exchange occurs, yielding...

A new series of polyoxometalate-based hybrids has been synthesized. These covalently linked organic−inorganic materials represent valuable elementary building blocks ready for postfunctionalization, using classical organic reactions and couplings. This approach is exemplified by the grafting an chromophore via a Sonogashira coupling.

A novel heteroleptic cyclometalated iridium(III) complex with one picolinic acid derivative bearing a pendant terminal alkynyl tether has been prepared following new synthetic route. This can be further engaged in palladium C–C coupling reactions, allowing its grafting to Keggin-type polyoxometalate and thus providing unique iridio-POM conjugate.

Electron transfer in strongly coupled photoactive hybrids built by direct combination of Dawson-type polyoxometalates with pyrene anchors and SWCNTs.

A series of redox tunable polyoxometalate–bodipy conjugates display variable charge transfer dynamics occuring down to 54 ps.

The photocatalytic recovery of noble metals on photosensitive semiconductors such as TiO2 is well-established for forming M/TiO2 but has notable drawbacks. suffers from low conversion efficiency due to significant recombination photogenerated electron–hole pairs. Its wide energy band gap (3.2 eV) also restricts excitation high-energy UV light, limiting its use with solar energy. This study proposes an efficient alternative using hybrid polyoxometalate (POM)–porphyrin copolymers the Ag and Pt...

Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains challenge for better understanding of its intrinsic reactivity. The first member third generation calixarene-based mono-copper “funnel” complexes described. ligand calix[6]arene capped by tren unit, hence presenting N 4 coordination confined cavity. Its Cu(II) were characterized electronic EPR spectroscopies. x-ray structure one them...

A new polyoxometalate-based organic–inorganic platform has been designed for further facile derivatization and covalent attachment of organic linkers; this is exemplified by the grafting a polypyridyl ligand.

You'll never walk alone: An auto-healing process of the first host-guest complex involving a polyoxometalate hybrid and cyclodextrin is reported. Indeed, this inclusion allows complete restoration anchored organic moiety released by basic stress, otherwise not fully reversible.

A Keggin-type POM is attached to gold or glassy carbon surfaces by electro(chemical) peptidic coupling. In addition demonstrating the robust attachment of POMs (by electrochemistry, XPS, and IRRAS), surface concentration, layer thickness, rate constant for electron transfer from have been measured. The use such complementary techniques mandatory characterize modified electrodes properly. Whatever grafting method, experimental conditions are found allow monolayer submonolayer coverage....

Polyoxometalates (POMs) are unconventional electro-active molecules with a great potential for applications in molecular memories, providing efficient processing steps onto electrodes available. The synthesis of the organic-inorganic polyoxometalate hybrids [PM$_{11}$O$_{39}$(Sn(C$_6$H$_4$)C$\equiv$C(C$_6$H$_4$)N$_2$)]$^{3-}$ (M = Mo, W) endowed remote diazonium function is reported together their covalent immobilization hydrogenated n-Si(100) substrates. Electron transport measurements...

Abstract 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 potentials. The functionalization POMs allows their integration hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control immobilisation on various substrates can be achieved. Owing to wide applicability diazonium route surface modification,...

The molybdenum core confers enhanced redox properties to a hybrid POM platform, which are further improved in the presence of acid.

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 spiropyran derivative (SP) has covalently grafted onto {PW11Sn} fragment via Sonogashira coupling successfully obtained. Alternatively, complex containing silicotungstate {PW11Si2} unit connected to entities characterized. purity of these assessed using several techniques,...

Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe hierarchical nanostructures using preformed by coordination-driven self-assembly a covalent organic-inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage presence charged subunits (POM, metal linker, and counterions) within metallomacrocycles, which drive their aggregation through intermolecular electrostatic...