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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[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.
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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-based hybrids and their integration into advanced molecular architectures or multi-scale assemblies as well as their immobilization onto surfaces. Valorisation of the remarkable redox properties of POMs in the fields of artificial synthesis and molecular electronic is especially considered.
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Currently available methodologies arguably lack the exquisite control required for producing metal-organic framework (MOF) thin films of sufficient quality for electronic applications. By directing MOF transfer with self-assembled monolayers (SAMs), we achieve very smooth, homogeneous, highly oriented, ultrathin films across millimeter-scale areas that display moderate conductivity likely due to electron hopping. Here, the SAM is key for directing the transfer thereby enlarging the number and nature of the substrates of choice. We have exploited this versatility to evolve from deposition onto standard Si and Au to nonconventional substrates such as ferromagnetic Permalloy. We believe that this strategy might be useful for the integration of MOFs as active interfaces in electronic devices.
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In the present article, the successful coassembly of spherical 6.2 nm maghemite (γ-Fe2O3) nanocrystals and giant polyoxometalates (POMs) such as 2.9 nm {Mo132} is demonstrated. To do so, colloidal solutions of oleic acid-capped γ-Fe2O3 and long-chain alkylammonium-encapsulated {Mo132 } dispersed in chloroform are mixed together and supported self-organized binary superlattices are obtained upon the solvent evaporation on immersed substrates. Both electronic microscopy and small angles X-ray scattering data reveal an AB-type structure and an enhanced structuration of the magnetic nanocrystals (MNCs) assembly with POMs in octahedral interstices. Therefore, {Mo132} acts as an efficient binder constituent for improving the nanocrystals ordering in 3D films. Interestingly, in the case of didodecyldimethylammonium (C12)-encapsulated POMs, the long-range ordered binary assemblies are obtained while preserving the nanocrystals magnetic properties due to weak POMs-MNCs interactions. On the other hand, POMs of larger effective diameter can be employed as spacer blocks for MNCs as shown by using {Mo132} capped with dioctadecyldimethylammonium (C18) displaying longer chains. In that case, it is shown that POMs can also be used for fine-tuning the dipolar interactions in γ-Fe2O3 nanocrystal assemblies.
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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). This enlarges the family of organic-inorganic polyoxomolybdate-based hybrids, which has been far less investigated than their related polyoxotungstates. The diazonium function allows for the electrochemical grafting on glassy carbon, and the K(Mo)Sn-modified electrode was further probed by cyclic voltammetry. The PMo11Sn core was found to be highly sensitive to protonation, and five bielectronic proton-coupled electron transfer processes were detected in the presence of an excess of TFA, thus corresponding to the injection of up to 10 electrons in the potential range between 0.15 and -0.45 V/SCE. The gain observed in the thermodynamic potentials is however detrimental to the apparent kinetics of the electron transfer, which drops from 500 s(-1) in the absence of acid to 12 s(-1) in the presence of an excess of TFA.
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Co/Fe Prussian Blue analogues are known to display both thermally and light induced electron transfer attributed to the switching between diamagnetic {Fe(II)LS(µ-CN)Co(III)LS} and paramagnetic {Fe(III)LS(µ-CN)Co(II)HS} pairs (LS = low spin; HS = high spin). In this work, a dinuclear cyanido-bridged Co/Fe complex, the smallest {Fe(µ-CN)Co} moiety at the origin of the remarkable physical properties of these systems, has been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered in solid state by light, temperature and solvent contents, is observed for the first time in a dinuclear complex.
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The local symmetry and local magnetic properties of 6â nm-sized, bimetallic, cyanide-bridged CsNiCr(CN)6 coordination nanoparticles 1 and 8â nm-sized, trimetallic, CsNiCr(CN)6@CsCoCr(CN)6 core-shell nanoparticles 2 were studied by X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The measurements were performed at the Ni(II), Co(II), and Cr(III) L2,3 edges. This study revealed the presence of distorted Ni(II) sites located on the particle surface of 1 that account for the uniaxial magnetic anisotropy observed by SQUID measurements. For the core-shell particles, a combination of the exchange anisotropy between the core and the shell and the pronounced anisotropy of the Co(II) ions is the origin of the large increase in coercive field from 120 to 890â Oe on going from 1 to 2. In addition, XMCD allows the relative orientation of the magnetic moments throughout the core-shell particles to be determined. While for the bimetallic particles of 1, alignment of the magnetic moments of Cr(III) ions with those of Ni(II) ions leads to uniform magnetization, in the core-shell particles 2 the magnetic moments of the isotropic Cr(III) follow those of Co(II) ions in the shell and those of Ni(II) ions in the core, and this leads to nonuniform magnetization in the whole nanoobject, mainly due to the large difference in local anisotropy between the Co(II) ions belonging to the surface and the Ni(II) ions in the core.
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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), [NaâP5W30O110]14-, stabilized with four different counterions, H+, K+, NH4+, and tetrabutylammonium (TBA+). We study the electron transport properties at the nanoscale (conductive atomic force microscopy, C-AFM) of molecular junctions formed by self-assembled monolayers (SAMs) of POMs electrostatically deposited on the ultraflat gold surface prefunctionalized with a positively charged SAM of amine-terminated alkylthiol chains. We report that the electron transport properties of P5W30-based molecular junctions depend on the nature of the counterions; the low-bias current (in the voltage range [-0.6 V; 0.6 V]) gradually increases by a factor of â¼100 by changing the counterion in the order: K+, NH4+, H+ and TBA+. From a statistical study (hundreds of current-voltage traces) using a simple analytical model for charge transport in nanoscale devices, we show that the energy position of the lowest unoccupied molecular orbital (LUMO) of P5W30 with respect to the Fermi energy of the electrodes increases from â¼0.4 eV to â¼0.7 eV and that the electrode coupling energy also increases from â¼0.05 to 1 meV in the same order from K+, NH4+, H+ to TBA+. We discuss several hypotheses on the possible origin of these features, such as a counterion-dependent dipole at the POM/electrode interface and counterion-modulated molecule/electrode hybridization, with, in both cases, the largest effect in the case of TBA+ counterions.
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Ouro , Eletrodos , Transporte de Elétrons , Microscopia de Força Atômica/métodosRESUMO
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 individually on a surface are still lacking. In this study we show that it is possible to periodically organize individual polyoxometalates thanks to their ordering by a new supramolecular assembly.
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Through an extensive set of SQUID magnetic measurements, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism, we have determined the nature of the metastable photomagnetic phase in the cyano-bridged 3D network Cs(2)Cu(7)[Mo(CN)(8)](4). The photomagnetic effect is induced by the photoconversion of Mo(IV) ions in low spin (LS) configuration (S = 0) into Mo(IV) ions in high spin (HS) configuration (S = 1). The magnetic and spectroscopic measurements fully support the LS to HS conversion, whereas the previously invoked charge transfer mechanism Mo(IV) + Cu(II) â Mo(V) + Cu(I) can be completely ruled out.
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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.
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We demonstrate the reversible in situ photoreduction of molecular junctions of a 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 â¼10, and this open-shell state is stable in the junction in air at room temperature. The analysis of a large current-voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetric current-voltage curves, controlled by the lowest unoccupied molecular orbital (LUMO) at 0.6-0.7 eV above the Fermi energy with â¼25% of the junctions having a better electronic coupling to the electrodes than the main part of the dataset. This analysis also shows that a small fraction (â¼18% of the dataset) of the molecules is already reduced. The UV light in situ photoreduced phosphomolybdate junctions systematically feature slightly asymmetric current-voltage behaviors, which is ascribed to the electron transport mediated by the single occupied molecular orbital (SOMO) nearly at resonance with the Fermi energy of the electrodes and by a closely located single unoccupied molecular orbital (SUMO) at â¼0.3 eV above the SOMO with a weak electronic coupling to the electrodes (â¼50% of the dataset) or at â¼0.4 eV but with a better electrode coupling (â¼50% of the dataset). These results shed light on the electronic properties of reversible switchable redox polyoxometalates, a key point for potential applications in nanoelectronic devices.
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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 nanoparticle self-assemblies (PtNP SAs) are synthesized in solution, including a series of polyoxometalates (POMs). The charge of the POM unit can be modified according to the nature of the central heteroatom while keeping its size constant. POM hybrids that display remote terminal thiol functions strongly anchor the PtNP surface to form robust SAs. IV curves, recorded by conductive AFM, show a decrease in Coulomb blockade as the dielectric constant of the POMs increases. In this system, charge transport across molecular junctions can be interpreted as variations in polarizability, which is directly related to the dielectric constant.
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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 covalent grafting of POM hybrids with remote carboxylic acid functions onto flat Si/SiO2 substrates. Special attention has been paid to the characterization of the molecular layer and to the description of the POM anchoring mode at the oxide interface through the use of various characterization techniques, including ellipsometry, AFM, XPS, and FTIR. Finally, electron transport properties were probed in a vertical junction configuration and energy level diagrams have been drawn and discussed in relation with the POM molecular electronic features inferred from cyclic-voltammetry, UV-visible absorption spectra, and theoretical calculations. The electronic properties of these POM-based molecular junctions are driven by the POM LUMO (d-orbitals) whatever the nature of the tether or the anchoring group.
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Designing new objects in the perspective of creating useful functionalities at the nanoscale has been the subject of intense research efforts during the last 20 years. Coordination nanoparticles (CNPs) emerged less than 10 years ago, opening new possibilities for the design of bistable molecule-based objects where magnetism may be controlled or tuned by an external perturbation (light irradiation, temperature change, magnetic field, etc.). Magnetic cyanide-bridged networks have been shown to possess the potential to be shaped as nanoparticles, leading to new functionalities. Light- and temperature-induced bistable nanoparticles were thus discovered. Luminescent CNPs were also prepared, demonstrating the large potential of these objects.
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Nanopartículas/química , Magnetismo , Tamanho da Partícula , Propriedades de Superfície , TemperaturaRESUMO
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 systems and studied the effect of the nature of the polyoxometalates (POMs) on the magnetic properties. In the present paper, we study the stability of this model binary assembly under heating at various temperatures. Indeed, especially if magnetic and/or transport properties are targeted, an annealing can be essential to change the phase of the nanocrystals in a more magnetic one and/or to desorb the organic capping of the nano-objects that can constitute an obstacle to the electronic communication between the nano-objects. We gave evidence that the maghemite organization in the binary assembly is maintained until 370°C under vacuum thanks to the presence of the POMs. This latter evolve in the phase MoO3, but still permits to avoid the aggregation of the nanocrystals as well as preserve their periodical arrangement. On the contrary, an assembly made of pure γ-Fe2O3 nanocrystals displays a clear aggregation of the nano-objects from 370°C, as attested by transmission and scanning electronic microscopies and confirmed by magnetic measurements. The stability of the magnetic nanocrystals in such POMs/nanocrystals assemblies opens the way to (i) the elaboration of new binary assemblies from POMs and numerous kinds of nanocrystals with a good control on the magnetic properties and to (ii) the investigation of new physical properties as exchange coupling, or magneto-transport in such systems.
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Prussian blue CsNiCr nanoparticles are used to decorate selected portions of a Si substrate. For successful grafting to take place, the Si surface needs first to be chemically functionalized. Low-dose focused ion beam patterning on uniformly functionalized surfaces selects those portions that will not participate in the grafting process. Step-by-step control is assured by atomic force and high-resolution scanning electron microscopy, revealing a submonolayer distribution of the grafted nanoparticles. By novel scanning Hall-probe microscopy, an in-depth investigation of the magnetic response of the nanoparticles to varying temperature and applied magnetic field is provided. The magnetic images acquired suggest that low-temperature canted ferromagnetism is found in the grafted nanoparticles, similar to what is observed in the equivalent bulk material.
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Cianetos/química , Nanopartículas/química , Silício/química , Magnetismo , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Propriedades de SuperfícieRESUMO
Spin-crossover coordination nanoparticles of the cyanide-bridged three-dimensional network Fe(pyrazine){Pt(CN) 4} were prepared at three different sizes using a microemulsion. The 14 nm particles present a transition centered around 265 K with a hysteresis of 6 K.
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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[triple bond, length as m-dash]C(C6H4)N2}]3- (M = Mo, W) endowed with a remote diazonium function is reported together with their covalent immobilization onto hydrogenated n-Si(100) substrates. Electron transport measurements through the resulting densely-packed monolayers contacted with a mercury drop as a top electrode confirms their homogeneity. Adjustment of the current-voltage curves with the Simmon's equation gives a mean tunnel energy barrier ΦPOM of 1.8 eV and 1.6 eV, for the Silicon-Molecules-Metal (SMM) junctions based on the polyoxotungstates (M = W) and polyoxomolybdates (M = Mo), respectively. This follows the trend observed in the electrochemical properties of POMs in solution, the polyoxomolybdates being easier to reduce than the polyoxotungstates, in agreement with lowest unoccupied molecular orbitals (LUMOs) of lower energy. The molecular signature of the POMs is thus clearly identifiable in the solid-state electrical properties and the unmatched diversity of POM molecular and electronic structures should offer a great modularity.
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Controlling the elaboration of Coordination Networks (CoNet) on surfaces at the nanoscale remains a challenge. One suitable technique is the Sequential Growth in Solution (SGS), which has the advantage to be simple, cheap and fast. We addressed two issues in this article: i) the controlled synthesis of ultra thin films of CoNet (thickness lower than 10 nm), and ii) the investigation of the influence of the precursors' concentration on the growth process. Si(100) was used because it is possible to prepare atomically flat Si-H surfaces, which is necessary for the growth of ultrathin films. We used, as a model system, the sequential reactions of K(4)[Fe(II)(CN)(6)] and [Ni(II)(H(2)O)(6)]Cl(2) that occur by the substitution of the water molecules in the coordination sphere of Ni(II) by the nitrogen atoms of ferrocyanide. We demonstrated that the nature of the deposited film depends mainly on the relative concentration of the anchoring sites versus the precursors' solution. Attenuated Total Reflection Fourier Transformed Infra Red (ATR-FTIR), X-ray reflectivity, X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM) were used to characterize the steps of the growth process.