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Layered transition metal compounds represent a major playground to explore unconventional electric or magnetic properties. In that framework, topochemical approaches that mostly preserve the topology of layered reactants have been intensively investigated to tune properties and/or design new materials. Topochemical reactions often involve the insertion or deinsertion of a chemical element accompanied by a change of oxidation state of the cations only. Conversely, cases where anions play the role of redox centers are very scarce. Here we show that the insertion of copper into two dimensional precursors containing chalcogen dimers (Q 2 ) 2- (Q=S, Se) can produce layered materials with extended (CuQ) sheets. The reality of this topochemical reaction is demonstrated here for different pristine materials, namely La 2 O 2 S 2 , Ba 2 F 2 S 2 , and LaSe 2 . Therefore, this work opens up a new synthetic strategy to design layered transition metal compounds from precursors containing polyanionic redox centers., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein we present an open-source program automating the post-treatment of solid-state ab initio calculations performed with VASP, the most used solid-state simulation package. The program plots Density of States (DOS) and Band Diagrams, enabling the user to conduct efficiently a detailed study of electronic properties of a material. Our tool includes a complete module dedicated to point defects studies, proposing various corrections which can be activated at will and innovative property calculations such as defect concentrations. This is the first program of its kind to offer a direct plot of the stability domain of the studied matrix with respect to its components' chemical potentials. We also implemented the retrieval of optical indices ɛ 1 and ɛ 2 , the computation of the refractive and extinction coefficients (n, k) and the reflexivity R of the material. All features of the piece of software are available through a thoroughly designed user-friendly, elegant and efficient Graphical User Interface (GUI) to be accessible to material scientists with various expertises, from both the experimental and theoretical sides. All figures are of publishable quality and can be customized as desired. © 2018 Wiley Periodicals, Inc., (© 2018 Wiley Periodicals, Inc.)

The luminescence properties of Gd 3+ or Tb 3+ ions at La and Sc sites were investigated in LaScO 3 with a distorted perovskite-type structure (ABO 3 ). Although the luminescence of lanthanide ions located at B sites is not common and has not been examined in detail, Gd 3+ or Tb 3+ luminescence from B sites and A sites is clearly observed in Gd 3+ - or Tb 3+ -doped LaScO 3 . The differences in the luminescence characteristics concern peak positions, peak shapes, and decay time, which are all influenced by the crystal field and the site symmetry. The UV luminescence of Gd 3+ at B sites shows a red shift compared to Gd 3+ at A sites, and the green luminescence of Tb 3+ at B sites contrasts with the blue-violet and green luminescence of Tb 3+ at A sites. The decay time of the luminescence from B sites is systematically longer than that from A sites in both the Gd 3+ and Tb 3+ cases.

Quantum dots (QDs) are very attractive materials for solar cells due to their high absorption coefficients, size dependence and easy tunability of their optical and electronic properties due to quantum confinement. Particularly interesting are PbS QDs owing to their broad spectral absorption until long wavelengths, their easy processability and low cost. Here, we used control of the PbS QD size to understand charge transfer processes at the interfaces of a NiO semiconductor and explain the optimal QD size in photovoltaic devices. Towards this goal, we have synthesized a series of PbS QDs with different diameters (2.8 nm to 4 nm) and investigated charge transfer dynamics by time resolved spectroscopy and their ability to act as sensitizers in nanocrystalline NiO based solar cells using the cobalt tris(4,4'-ditert-butyl-2,2'-bipyridine) complex as a redox mediator. We found that PbS QDs with an average diameter of 3.0 nm show the highest performance in terms of efficient charge transfer and light harvesting efficiency. Our study showed that hole injection from the PbS QDs to the NiO valence band (VB) is an efficient process even with low injection driving force (-0.3 eV) and occurs in 6-10 ns. Furthermore we found that direct electrolyte reduction (photoinduced electron transfer to the cobalt redox mediator) also occurs in parallel to the hole injection with a rate constant of similar magnitude (10-20 ns). In spite of its large driving force, the rate constant of the oxidative quenching of PbS by Co(iii) diminishes more steeply than hole injection on NiO when the diameter of PbS increases. This is understood as the consequence of increasing the trap states that limit electron shift. We believe that our detailed findings will advance the future design of QD sensitized photocathodes.

Nickel carbodiimide (NiCN 2 ) was synthesized using a two-step precipitation-decomposition route leading to a brown powder with gypsum-flower-like morphology and a large specific surface area (75 m 2 /g). This layered material crystallizes in the 2H structure type of delafossite (space group P6 3 /mmc), which is built upon infinite 2 / ∞ [NiN 2 ] layers connected by linear carbodiimide ([N═C═N] 2- ) bridges. An X-ray diffraction Rietveld refinement and thermal analyses pointed out some nickel deficiencies in the material, and band structure calculations carried out on the defect compound predicted p-type conductivity in relation to a slight amount of N 2- . This p-type conductivity was demonstrated by electrochemical impedance spectroscopy measurements, and a flat band potential of 0.90 V vs SCE at pH 9.4 was measured. This value, which is more positive than those of CuGaO 2 and CuCrO 2 delafossite oxides and NiO, prompted us to test NiCN 2 nanoparticles as a photocathode in p-type dye-sensitized solar cells.

An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnC 2 O 3 H 2 ) n , which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal-oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

The physical properties of doped multifunctional compounds are commonly tuned by controlling the amount of dopants, but this control is limited because all the properties are influenced simultaneously by this single parameter. Here, we present a strategy that enables the fine-tuning of a specific combination of properties by controlling the reduction of dopants. The feasibility of this approach was demonstrated by optimizing the near-IR photoluminescence of strontium titanate SrTiO 3 :Ni for potential applications in biomedicine for a range of absorbance in the visible/near-IR region. We discussed how material properties, such as luminescence, conductivity, or photocatalytic properties can be designed by carefully controlling the ratio of dopants in different oxidation states., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Novel melilite-type Ca2Ga2SiO7:Eu(3+) red-emitting phosphors with different Eu(3+) contents were synthesized via high-temperature solid-state reaction. The crystal structure, optical absorption, and photoluminescence properties were investigated, while density functional theory calculations were performed on the host lattice. The excitation spectra indicate that phosphors can be effectively excited by near-UV light for a potential application in white-light-emitting diodes. Because of the abnormally high intensity emission at about 700 nm arising from the (5)D0 → (7)F4 transition of Eu(3+), the phosphors Ca2Ga2SiO7:Eu(3+) show a deep-red emission with chromaticity coordinates (0.639, 0.358).

Optical and electrical characteristics of solid materials are well-known to be intimately related to the presence of intrinsic or extrinsic defects. Hence, the control of defects in semiconductors is of great importance to achieve specific properties, for example, transparency and conductivity. Herein, a facile and controllable reduction method for modulating the defects is proposed and used for the case of p-type delafossite CuCrO2 nanoparticles. The optical absorption in the infrared region of the CuCrO2 material can then be fine-tuned via the continuous reduction of nonstoichiometric Cu(II), naturally stabilized in small amounts. This reduction modifies the concentration of positive charge carriers in the material, and thus the conductive and reflective properties, as well as the flat band potential. Indeed, this controllable reduction methodology provides a novel strategy to modulate the (opto-) electronic characteristics of semiconductors.

Sensitized NiO based photocathode is a new field of investigation with increasing scientific interest in relation with the development of tandem dye-sensitized solar cells (photovoltaic) and dye-sensitized photoelectrosynthetic cells (solar fuel). We demonstrate herein that PbS quantum dots (QDs) represent promising inorganic sensitizers for NiO-based quantum dot-sensitized solar cells (QDSSCs). The solar cell sensitized with PbS quantum dot exhibits significantly higher photoconversion efficiency than solar cells sensitized with a classical and efficient molecular sensitizer (P1 dye = 4-(Bis-{4-[5-(2,2-dicyano-vinyl)-thiophene-2-yl]-phenyl}-amino)-benzoic acid). Furthermore, the system features an IPCE (Incident Photon-to-Current Efficiency) spectrum that spreads into the infra-red region, reaching operating wavelengths of 950 nm. The QDSSC photoelectrochemical device works with the complexes tris(4,4'-ditert-butyl-2,2'-bipyridine)cobalt(III/II) redox mediators, underscoring the formation of a long-lived charge-separated state. The electrochemical impedance spectrocopy measurements are consistent with a high packing of the QDs upon the NiO surface, the high density of which limits the access of the electrolyte and results in favorable light absorption cross-sections and a significant hole lifetime. These notable results highlight the potential of NiO-based photocathodes sensitized with quantum dots for accessing and exploiting the low-energy part of the solar spectrum in photovoltaic and photocatalysis applications.

A promising general approach is proposed that enables the controlled reduction of dopants to tune the photoluminescence properties of single-phase materials. The change of oxidation state of dopants in phosphor phases leads to different emission colors that can be finely tuned. This approach was illustrated with the progressive reduction of the red phosphor SrAl2O4:Eu(3+) to green phosphor SrAl2O4:Eu(2+) to target yellow luminescence., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles.

Bulk compounds, prepared via the ceramic route, related to Cu2ZnSnSe4 (CZTSe), a material considered for use in photovoltaic devices, were investigated using NMR spectroscopy, electron-probe microanalyses and X-ray diffraction. These materials adopt the kesterite structure regardless of the Cu and Zn contents. It is also shown that the stability domain of the copper-poor quaternary phases is wider for selenide derivatives than for sulphides. Finally, the Cu/Zn disorder level in CZTSe is found to be higher when the samples are quenched, which is reminiscent of the behaviour of the parent sulphide compounds CZTS.

In the presence of "Ag2O" as a promoter, γ-MnO2 traps dihydrogen in its (2 × 1) and (1 × 1) tunnels. The course of this reaction was examined by analyzing the X-ray diffraction patterns of the HxMnO2/"Ag2O" system (0 ≤ x < 1) on the basis of pair distribution function and density functional theory (DFT) analyses. Hydrogen trapping occurs preferentially in the (2 × 1) tunnels of γ-MnO2, which is then followed by that in the (1 × 1) tunnels. Our DFT analysis shows that this process is thermodynamically favorable.

Polycrystalline yttrium iron garnet (Y3Fe5O12, hereafter labeled YIG) has been synthesized by solid-state reaction, characterized by X-ray diffraction, Mössbauer spectroscopy, and UV-vis-NIR diffuse reflectance spectroscopy, and its optical properties from room temperature (RT) to 300 °C are discussed. Namely, its greenish color at RT is assigned to an O(2-) → Fe(3+) ligand-to-metal charge transfer at 2.57 eV coupled with d-d transitions peaking at 1.35 and 2.04 eV. When the temperature is raised, YIG displays a marked thermochromic effect; i.e., the color changes continuously from greenish to brownish, which offers opportunities for potential application as a temperature indicator for everyday uses. The origin of the observed thermochromism is assigned to a gradual red shift of the ligand-to-metal charge transfer with temperature while the positioning in energy of the d-d transitions is almost unaltered. Attempts to achieve more saturated colors via doping (e.g., Al(3+), Ga(3+), Mn(3+), ...) remained unsuccessful except for chromium. Indeed, Y3Fe5O12:Cr samples exhibit at RT the same color than the undoped garnet at 200 °C. The introduction of Cr(3+) ions strongly impacts the color of the Y3Fe5O12 parent either by an inductive effect or, more probably, by a direct effect on the electronic structure of the undoped material with formation of a midgap state.

The material Cu2ZnSn(S,Se)4 (CZTS) offers a promising indium-free alternative to Cu(In,Ga)Se2 for the absorber layer in thin-film solar cells. It is known that the highest solar energy conversion efficiencies are reached for Cu-poor, Zn-rich CZTS compositions and that too much disorder at the Cu and Zn sites can have a negative impact on the device performance. In this article, we investigate the structures of [VCu + ZnCu] A-type and [2ZnCu + ZnSn] B-type defect complexes and their impact on the long-range Cu/Zn disorder. To that end, we use (119)Sn, (65)Cu, and (67)Zn solid-state NMR and Raman spectroscopy to characterize powdered CZTS samples. For both A- and B-type substitutions, our NMR investigations demonstrate the clustering of the complexes. Moreover, we show that (A+B)-type compounds should be considered as A-type and B-type compounds, since no interaction seems to exist between [VCu + ZnCu] and [2ZnCu + ZnSn] defect complexes. In addition, it is worth noting that [2ZnCu + ZnSn] complexes have only a minor impact on the level of disorder at the Cu and Zn sites. In contrast, [VCu + ZnCu] complexes seem to restrain the random distribution of Cu at the Zn site and of Zn at the Cu site; i.e., the long-range Cu/Zn disorder. Raman characterization of the CZTS samples was also conducted. The Q = I287/I303 and the newly introduced Q' = I338/(I366 + I374) ratios determined from Raman spectra collected at 785 nm turn out to be very sensitive to the level of Cu/Zn disorder. Moreover, they can be used to differentiate the nature of the substitution in slow-cooled materials.

Cu/Zn disorder in the kesterite Cu2ZnSnS4 derivatives used for thin film based solar cells is an important issue for photovoltaic performances. Unfortunately, Cu and Zn cannot be distinguished by conventional laboratory X-ray diffraction. This paper reports on a resonant diffraction investigation of a Cu2ZnSnS4 single crystal from a quenched powdered sample. The full disorder of Cu and Zn in the z = 1/4 atomic plane is shown. The structure, namely disordered kesterite, is then described in the I42m space group.

For the very first time, (67)Zn, (119)Sn and (65)Cu NMR investigations have been carried out on Cu2ZnSnS4 derivatives (CZTS) for photovoltaic applications. NMR spectroscopy is shown to be sensitive enough to probe the Cu/Zn disorder within the kesterite structure of the studied compounds. In addition, reference spectra of Cu2ZnSnS4 are provided, and experimental (67)Zn and (65)Cu parameters are compared with ab initio calculations.

Ultrathin Ag2Mo3O10·2H2O nanowires (NWs) were synthesized by soft chemistry under atmospheric pressure from a hybrid organic-inorganic polyoxometalate (CH3NH3)2[Mo7O22] and characterized by powder X-ray diffraction, DSC/TGA analyses, FT-IR and FT-Raman spectroscopies, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Their diameters are a few tens of nanometers and hence much thinner than that found for silver molybdates commonly obtained under hydrothermal conditions. The optical properties of Ag2Mo3O10·2H2O NWs before and after UV irradiation were investigated by UV-vis-NIR diffuse reflectance spectroscopy revealing, in addition to photoreduction of Mo(6+) to Mo(5+) cations, in situ photogeneration of well-dispersed silver Ag(0) nanoparticles on the surface of the NWs. The resulting Ag@Ag2Mo3O10·2H2O heterostructure was confirmed by electron energy-loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), and Auger spectroscopy. Concomitant reduction of Mo(6+) and Ag(+) cations under UV excitation was discussed on the basis of electronic band structure calculations. The Ag@Ag2Mo3O10·2H2O nanocomposite is an efficient visible-light-driven plasmonic photocatalyst for degradation of Rhodamine B dye in aqueous solution.

For the very first time, sulfonium polyoxometalate (POM) assemblies are shown to develop efficient solid-state photochromism in ambient conditions. The optical properties of the already known Rb(0.75)(NH(4))(5.25)[(Mo(3)O(8))(2)O(O(3)PC(CH(2)S(CH(3))(2))OPO(3))(2)]·8H(2)O (1) and a new material (Me(3)S)(4)[Mo(8)O(26)] (2) under UV excitation are investigated by diffuse reflectance spectroscopy, revealing that the color change effect is highly tunable playing with the nature of the POM. A mechanism involving the photoreduction of Mo(6+) cations associated with electron transfers from the sulfonium cations toward the POMs is proposed.

Polyoxometalates covalently linked to one or two spiropyran entities have been isolated. These organic-inorganic hybrids exhibit multi-electrochromic and photochromic properties.

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions., (© 2011 American Chemical Society)

Two new hybrid organic-inorganic molybdates based on layered (2/∞)[Mo(n)O(3n+1)](2-) blocks and organoammonium cations (+)(Me(x)H(3-x)N)(CH(2))(6)(NH(3-x)Me(x))(+) (x = 0-1), namely, (H(3)N(CH(2))(6)NH(3))[Mo(7)O(22)]·H(2)O (1) and (MeH(2)N(CH(2))(6)NH(2)Me)[Mo(9)O(28)] (2), have been synthesized under hydrothermal conditions. The (2/∞)[Mo(9)O(28)](2-) unit in 2 is an unprecedented member of the (2/∞)[Mo(n)O(3n+1)](2-) family with the n value extended to 9. The structural filiation between the (2/∞)[Mo(n)O(3n+1)](2-) (n = 5, 7, 9) blocks is well established, and their structural similarity with the (2/∞)[MoO(3)] slabs in α-MoO(3) is also discussed. Single-crystal X-ray analyses show that the (2/∞)[Mo(n)O(3n+1)](2-) layers in 1 and 2 are pillared in the three-dimensional networks by the organic cations with a similar connection at the organic-inorganic interface. In addition, a correlation between the topology of the (2/∞)[Mo(n)O(3n+1)](2-) blocks in 1 and 2 and the overall sizes of the associated organic cations is pointed out. Finally, the efficiency of Fourier transform Raman spectroscopy to easily discriminate the different (2/∞)[Mo(n)O(3n+1)](2-) blocks (n = 5, 7, 9) in hybrid organic-inorganic layered molybdate materials is clearly evidenced.

A new concept of photoresponsive composites has been elaborated by intimately connecting a Photochromic Phase (PP), (H(2)DABCO)(2)(HDMA)(0.5)Na(0.75)(H(3)O)(0.75)[Mo(8)O(27)]·3H(2)O (1), with a second hybrid organic-inorganic molybdate material, (H(2)DABCO)(HDABCO)[Fe(OH)(6)Mo(6)O(18)]·4H(2)O (2) acting as an Oxidation Catalytic Phase (OCP) toward the former once photoexcited. The association of both the PP and the OCP in the composite drastically improves the bleaching process of the PP alone because of efficient electronic transfers through the OCP-PP interface without affecting significantly its photoinduced color change characteristic. Two OCP-PP composites with different PP weight percents have been obtained by associating 1 with 2. The optical properties of these composites before and after UV irradiation have been investigated by Diffuse Reflectance Spectroscopy, and the strong impact of the OCP on the fading kinetics of the PP has been clearly highlighted.

A series of compounds of Co(1-x)Mg(x)MoO(4) compositions has been prepared by a conventional ceramic route. The members of the whole solid solution exhibit a reversible first-order phase transition which was probed by using thermal expansion and low-temperature reflectivity techniques. Whereas the α → β transition temperature evolves linearly on warming from 435 to 200 °C with x going from 0 to 0.9, the β → α transition temperature variation falls down on cooling from -40 °C to -140 °C going from CoMoO(4) to Co(0.1)Mg(0.9)MoO(4) with an asymptotic evolution. The phase transition temperatures have been explained on the basis of a crystal polarization effect under substitution of Mg for Co. Thus, from an applicative point of view, new thermochromic pigments with tunable transition temperatures are here proposed.

We investigate the reactivity of MoO(4)(2-) toward six organoammonium cations (+)(Me(3-x)H(x)N)(CH(2))(2)(NH(y)Me(3-y))(+) (x, y = 1-3) at different synthesis temperatures ranging from 70 to 180 °C. A total of 16 hybrid organic-inorganic materials have been synthesized at an initial pH of 2, via ambient pressure and hydrothermal routes, namely, (H(2)en)[Mo(3)O(10)]·H(2)O (1), (H(2)en)[Mo(3)O(10)] (2), (H(2)en)[Mo(5)O(16)] (3), (H(2)MED)(2)[Mo(8)O(26)]·2H(2)O (4), (H(2)MED)[Mo(5)O(16)] (5), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (6), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (7), (N,N'-H(2)DMED)(2)[Mo(8)O(26)] (8), (N,N'-H(2)DMED)[Mo(5)O(16)] (9), (H(2)TriMED)(2)[Mo(8)O(26)]·4H(2)O (10), (H(2)TriMED)(2)[Mo(8)O(26)]·2H(2)O (11), (H(2)TriMED)[Mo(7)O(22)] (12), (H(2)TMED)(2)[Mo(8)O(26)]·2H(2)O (13), (H(2)TMED)(2)[Mo(8)O(26)] (14), (H(2)TMED)(2)[Mo(8)O(26)] (15), and (H(2)TMED)[Mo(7)O(22)] (16). All of these compounds contain different polyoxomolybdate (Mo-POM) blocks, i.e., discrete β-[Mo(8)O(26)](4-) blocks in 6, 10, 13, 14, (1)/(∞)[Mo(3)O(10)](2-), and (1)/(∞)[Mo(8)O(26)](4-) polymeric chains in 1, 2, 4, 7, 8, and 15, respectively, and (2)/(∞)[Mo(5)O(16)](2-) and (2)/(∞)[Mo(7)O(22)](2-) layers in 3, 5, 9, 12, and 16, respectively. The structures of 5, 9, and 14 have been resolved by single-crystal X-ray analyses. The characterization of the different Mo-POM blocks in 1-16 by Fourier transform Raman spectroscopy is reported. The impact of the synthesis temperature on both the composition and topology of the Mo-POM blocks is highlighted.

We report here for the first time on the synthesis of nanoparticles of the p-type transparent conductor LaOCuS. Nanoparticles were obtained via a solvothermal route in ethylenediamine with dehydrated lanthanum chloride (LaCl(3).7H(2)O), copper monooxide, and elemental sulfur as precursors. Powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy ascertained our sample to be of high purity, while laser diffractometry evidenced a monodisperse particle size distribution centered on 126 nm. The absorption spectrum and the current-potential curves recorded under chopped illumination asserted the optical transparency and the p-type electronic conductivity of our LaOCuS nanoparticles.

Porous and nanostructured thin films of NiO (3.5 microm thick) were prepared on FTO coated glass by annealing nickel acetate films obtained by recrystallization under hydrothermal conditions in the presence of hexamethylenetetramine. The photovoltaic performances of the NiO films were optimized with coumarin C343 as sensitizer and iodide/triodide as redox mediator and led to the following values of V(OC), J(SC), ff, and eta: 117 mV, 0.88 mA/cm(2), 0.28, and 0.036% respectively, under AM 1.5. With the improved PMI-NDI dyad as sensitizer and the tris(4,4'-bis(tertbutyl)bipyridine) cobalt(II/III) couple as redox mediator, the overall photoconversion efficiency reached 0.16%. An essential advantage of this procedure lies in its good reproducibility offering a reliable strategy to test new dyes and other parameters to improve the photoconversion efficiency of this new type of DSSC.

The synthesis of lanthanum phosphates in molten LiCl-KCL eutectic was chosen to address the preliminary treatment of chlorinated wastes containing fission products that are already present in a Li/Cl eutectic. The obtained monazite compound shows interesting properties to be considered as a good candidate to trap lanthanum for a long-time. The synthesis route based on LaCl(3) reaction with NH(4)H(2)PO(4) in a stoichiometric amount is a key point to obtain monazite as a pure phase. Hence, the salt composition is not modified during the synthesis reaction. The chemical reactivity of ammonium dihydrogenphosphate (NH(4)H(2)PO(4), hereafter abbreviated ADP) toward lanthanum chloride (LaCl(3)) in molten LiCl-KCl eutectic is probed by NMR spectroscopy to follow the formation of LaPO(4). Formally, a direct transformation of the two aforementioned precursors into LaPO(4), NH(4)Cl and HCl can be discarded on the basis of the low thermal stability of ADP. To shed some light on the formation of LaPO(4), in situ and ex situ NMR experiments were carried out on LiCl-KCl/LaCl(3)/ADP, as well as LiCl-KCl/ADP, KCl/ADP, and LiCl/ADP mixtures. First, the reactivity of the precursors in contact with the eutectic was studied from room temperature to 600 degrees C by means of (31)P, (35)Cl, and (139)La high temperature NMR. Second, ex situ room temperature magic angle spinning (MAS) and RadioFrequency driven recoupling (RFDR) (31)P solid-state NMR experiments were carried out on solid samples prepared in different conditions (i.e., temperature and atmosphere) and quenched at room temperature to identify frozen intermediate species in their metastable state. On the basis of this approach, we propose a model for the LaPO(4) formation based on a multistep mechanism which highlights the strong reactivity of ADP toward the alkaline salts but without final change in the composition of the solvent.

The excellent photochromic properties of (H(2)DABCO)(2)(HDMA)(0.5)Na(0.75)(H(3)O)(0.75)[Mo(8)O(27)] x 3 H(2)O (4), a new member of the (H(2)DABCO)(2)(A)(x)[Mo(8)O(27)] x n H(2)O series, are compared with those of (H(2)DABCO)(2)(NH(4))(2)[Mo(8)O(27)] x 4 H(2)O (1), (H(2)DABCO)(2)(H(2)pipz)[Mo(8)O(27)] (2), and (H(2)pipz)(3)[Mo(8)O(27)] (3). All these powdered materials turn from white to purple under illumination at 365 nm, which is associated with photoreduction of Mo(6+) cations into Mo(5+) cations. We show that the rates of coloration, which increase in the order 1 < 3, 2 < 4, are related to the decrease in the concentration of reducible Mo(6+) centers with irradiation time and follow a second-order reaction law because the event of light absorption at a reducible Mo(6+) site does not necessarily coincide with that of the N(+)-H bond breaking in the N(+)-H...O hydrogen bond associated with the Mo(6+) site. First-principles density functional electronic structure calculations were carried out to find that this trend correlates with the homolytic dissociation energies of the N(+)-H bonds in the organic cations HDMA(+), H(2)pipz(2+), H(2)DABCO(2+), and NH(4)(+). This observation is consistent with a photochromic mechanism based on the homolytic cleavage of N(+)-H bonds rather than on the heterolytic cleavage of N(+)-H bonds.

The optical properties of Eu-activated (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66 materials have been determined after the structural reinvestigation of the hypothetical Ba 13Al 22Si 10O 66 material on the basis of the Gebert's model. The white fluorescence and phosphorescence of the (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66:Eu series result from the existence of two broad emission bands associated with (8)H-4f(6)5d(1)-->(8)S-4f(7) transitions peaking at 534 and 438 nm, the intensities of which may be tuned at room temperature via the control of the europium concentration and the substitution of Sr for Ba. This suggests the possibility to adjust the emission of the material to white LED requisites.

The members of the CuMo1-xWxO4 series (0alpha transition can occur between 260 and 360 K, and the alpha-->gamma transition between 175 and 275 K as a function of x. The control of the alpha/gamma transition temperatures with x is related to the larger propensity of tungsten compared to molybdenum, to adopt a tetrahedral environment.

The discrimination between atomic species in light-element materials is a challenging question. An archetypal example is the resolution of the Al/Si ordering in aluminosilicates. Only an average long-range order can be deduced from powder X-ray or neutron diffraction, while magic-angle-spinning NMR provides an accurate picture of the short-range order. The long- and short-range orders thus obtained usually differ, hence raising the question of whether the difference between local and extended orders is intrinsic or caused by the difficulty of obtaining an accurate picture of the long-range order from diffraction techniques. In this communication we resolve this question for the monoclinic phases of BaAl2Si2O8 and SrAl2Si2O8 on the basis of 27Al NMR measurements and ab initio simulation of electric field gradient. Although the long- and short-range orders deduced from our XRD and NMR experiments differ, they become similar when the XRD atomic positions are optimized by ab initio electronic structure calculations.

Prompted by our interest in new photochromic organic-inorganic hybrid materials, the reactivity of [Mo7O24]6- toward a structure-directing reagent diamine such as 1,4-diazabicyclo[2.2.2]octane (DABCO) and piperazine (pipz) has been investigated, and three new molybdenum(VI)-containing compounds, namely, (H2DABCO)3[Mo7O24].4H2O (1), (H2DABCO)[Mo3O10].H2O (2), and (H2DABCO)2(NH4)2[Mo8O27].4H2O (3), have been synthesized and characterized. New synthetic routes to achieve the known compounds (H2DABCO)2(H2pipz)[Mo8O27] (4), (H2pipz)3[Mo8O27] (5), and (H2DABCO)2[Mo8O26].4H2O (6) are also reported. All of these compounds contain different poly(oxomolybdate) clusters, i.e., discrete [Mo7O24]6- blocks in 1, infinite polymeric chains 1/infinity[Mo3O10]2- in 2, 1/infinity[Mo8O27]6- in 3-5, and 1/infinity[Mo8O26]4- in 6, associated in a tridimensional assembly by hydrogen bonds with H2DABCO2+ and/or H2pipz2+ cations. Interconversion pathways and chemical factors affecting the stabilization of the different species are highlighted and discussed. At the opposite of 6, compounds 1-5 show photochromic behavior under UV excitation. Namely, compounds 1-5 shift from white or pale yellow to pale pink, reddish brown, or purple under UV illumination depending on the chemical nature of the mineral framework, with the kinetics of the color change being dictated by the nature of the organic component and by the organic-inorganic interface.

The syntheses and structure determinations by means of single-crystal X-ray diffraction of commensurate (C(6)H(14)N(2))(2)[Mo(8)O(26)] * 4H(2)O and incommensurate (C(6)H(14)N(2))(2)[Mo(8)O(26)] * 4.66H(2)O, two new organic-inorganic hybrid compounds based on polyoxomolybdates and differing in their solvent content, are reported. Given the important disorder observed in the latter compound, only a combination of non-harmonic waves, crenel functions and TLS tensors offered a good modelling of the structure. (C(6)H(14)N(2))(2)[Mo(8)O(26)] * nH(2)O results from the self-assembly of [Mo(8)O(26)](4-) anionic chains, C(6)H(14)N(2)(2+) (H(2)DABCO(2+)) cations and water molecules. The [Mo(8)O(26)](4-) chain is built from gamma-[Mo(8)O(28)](8-) octamolybdate clusters, connected to each other through corner sharing. In both compounds, the [Mo(8)O(26)](4-) chains are separated, in a similar way, by the H(2)DABCO(2+) subunits, acting as charge-compensating cations, and by the water molecules. The orientation of the H(2)DABCO(2+) cations is shown to be different from what has been observed previously in monoclinic (H(2)DABCO)(2)[Mo(8)O(26)] * 4H(2)O, and therefore to give a different network of hydrogen bonds.

How indices of refraction n(omega) of insulating solids are affected by the volume dilution of an optical entity and the mixing of different, noninteracting simple solid components was examined on the basis of the dielectric function epsilon(1)(omega) + iepsilon(2)(omega). For closely related insulating solids with an identical composition and the formula unit volume V, the relation [epsilon(1)(omega) - 1]V = constant was found by combining the relation epsilon(2)(omega)V = constant with the Kramers-Kronig relation. This relation becomes [n(2)(omega) - 1]V = constant for the index of refraction n(omega) determined for the incident light with energy less than the band gap (i.e., h omega < E(g)). For a narrow range of change in the formula unit volume, the latter relation is well approximated by a linear relation between n and 1/V.

On the basis of first-principles electronic band structure theory, we calculated the refractive indices of the zinc blende and wurtzite structures of the chalcogenides ZnQ and CdQ (Q = O, S, Se, Te) and analyzed their trends by calculating the total absorption power per unit formula. The calculated refractive indices are in good agreement with the available experimental data. The total absorption power per formula unit is found to allow one to distinguish the effect of the chromophore from that of the cell volume on the refractive indices of insulating inorganic compounds.

In an effort to gain insight into how optical properties of insulating materials are affected by a change in chemical composition, we investigated the dielectric functions of titanium dioxide, TiO(2), and its fluorine-substituted phases, TiOF(2) and TiF(4), by electron energy loss spectroscopy measurements and density functional theory electronic band structure calculations. The refractive indices of these compounds are found to be inversely proportional to their cell volumes per formula unit. This observation was explained by employing the concept of optical channels. Our study indicates that the light-scattering properties of insulating compounds can be controlled by modifying their cell volumes.

The olivine-type compounds LiMPO4 (M = Mn, Fe, Co, Ni) consist of MO4 layers made up of corner-sharing MO6 octahedra of high-spin M2+ ions. To gain insight into the magnetic properties of these phosphates, their spin exchange interactions were estimated by spin dimer analysis using tight binding calculations and by electronic band structure analysis using first principles density functional theory calculations. Three spin exchange interactions were found to be important for LiMPO4, namely, the intralayer superexchange J1, the intralayer super-superexchange Jb along the b-direction, and the interlayer super-superexchange J2 along the b-direction. The magnetic ground state of LiMPO4 was determined in terms of these spin exchange interactions by calculating the total spin exchange interaction energy under the classical spin approximation. In the spin lattice of LiMPO4, the two-dimensional antiferromagnetic planes defined by the spin exchange J1 are antiferromagnetically coupled by the spin exchange J2, in agreement with available experimental data.

On the basis of first principles electronic structure calculations, we determined the dielectric functions, the refractive indices, and the extinction coefficients of the seven different phases of TiO(2) and then examined why the refractive index is related to the density by the empirical Glastone-Dale equation. The zero frequency limit of the refractive index, n(0), is found to be a good approximation for the refractive index n determined around 2 eV. Our study indicates that the major factor influencing n in a series of closely related systems is the structure compactness. This finding suggests a way of preparing new UV absorbers with low refractive index.

Under ambient condition PdSe2 has the PdS2-type structure. The crystal structure of PdSe2 under pressure (up to 30 GPa) was investigated at room temperature by X-ray diffraction in an energy-dispersive configuration using a diamond anvil cell with a mixture of water/ethanol/methanol as a pressure transmitting medium. A reversible structural transition from the PdS2-type to the pyrite-type structure occurs around 10 GPa, and the applied pressure reduces the spacing between adjacent 2/proportional to [PdSe2] layers of the PdS2-type structure to form the three-dimensional lattice of the pyrite-type structure. First principles and extended Hückel electronic band structure calculations were carried out to confirm the observed pressure-induced structural changes. We also examined why the isoelectronic analogues NiSe2 and PtSe2 adopt structures different from the PdS2-type structure on the basis of qualitative electronic structure considerations.

We examined why the 1T-VS(2) layer of the layered compound Sr(6)V(9)S(22)O(2) has the x superstructure in terms of electronic band structure calculations and metal-metal bonding across the shared edges of adjacent VS(6) octahedra. On the basis of this analysis we explored how the anomalous magnetic and transport properties of Sr(6)V(9)S(22)O(2) can be explained. Our work shows that the x superstructure is not caused by a charge density wave instability associated with Fermi surface nesting but by the metal-metal bonding through the shared edges of adjacent VS(6) octahedra. The weak and strong electron localizations observed for Sr(6)V(9)S(22)O(2) were discussed in terms of three-center two-electron and two-center two-electron V-V bonds in the 1T-VS(2) layers.

The new monoclinic IrTe2 phase m-IrTe2 was synthesized under pressure, and its structure was determined by X-ray powder diffraction. The relative stabilities of the three known and three hypothetical IrTe2 polymorphs were discussed on the basis of tight binding electronic band structure calculations. m-IrTe2 exhibits structural features of both CdI2- and pyrite-type IrTe2 phases and is expected to be nearly as stable as that of the CdI2-type IrTe2. The hypothetical IrS2- and ramsdellite-type IrTe2 phases are predicted to be more stable than the CdI2-type IrTe2.

The structure of nonapotassium cerium tetraphosphorus hexadecasulfide, a zero-dimensional material isostructural with Rb(9)CeP(4)Se(16), is reported.

Bi metal dissolves in excess molten phosphorus selenide at 500 degrees C to yield black, rodlike, air- and water-stable beta-Bi(4)(P(2)Se(6))(3) crystals. The phase crystallizes in the triclinic space group P&onemacr; (No. 2) with the room-temperature cell parameters a = 12.2303(8) Å, b = 6.7640(4) Å, c = 17.866 Å, alpha = 90.493(6) degrees, beta = 94.133(6) degrees, and gamma = 91.163(6) degrees. The new structure is a complicated, three-dimensional framework built from [Bi(4)Se(22)] ribbons connected to each other by sharing selenium atoms. The [P(2)Se(6)](4)(-) ethane-like units are found inside and between the [Bi(4)Se(22)] ribbons. The compound is a semiconductor with a band gap of 1.32 eV. It melts with decomposition at 512 degrees C, converting partially to Bi(2)Se(3) and a P(x)()Se(y)() glassy material. Far-IR and Raman spectra show characteristic stretches for the [P(2)Se(6)](4)(-) ligand and Bi-Se vibrations. The structural and chemical relationships of this compound with the alpha-form are discussed.

A remarkable autofragmentation/rearrangement sequence results in the unprecedented formation of inorganic concave cyclic anion [(NiPS 4 ) 3 ] 3- (structure shown on the right) upon dissolving the potassium salt of the charged mineral polymer 1 ∞ [NiPS 4 ] - in DMF; the initial complex fluid has a transient anisotropic texture that can be identified by optical microscopy under polarized light. In contrast, the complex fluid that results upon dissolving 1 ∞ [PdPS 4 ] - is stable up to 323 K as persistent, flexible, charged chains., (© 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)

The reaction of Pd with a molten mixture of A(2)Q(x)()/P(2)Q(5)/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K(4)Pd(PS(4))(2) (I), Cs(4)Pd(PSe(4))(2) (II), and Cs(10)Pd(PSe(4))(4) (III) and the solid-state KPdPS(4) (IV), K(2)PdP(2)S(6) (V), and Cs(2)PdP(2)Se(6) (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P&onemacr; (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, alpha = 87.777(8) degrees, beta = 81.581(8) degrees, gamma = 84.429(9) degrees, and Z = 1. Compound II crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, beta = 92.21(2) degrees, and Z = 2. Compound III crystallizes in the tetragonal space group P&fourmacr;2c (No. 112) with a = b = 13.949(2) Å, c = 11.527(2) Å, and Z = 4. Compound IV crystallizes in the tetragonal space group P4(2)/mnm (No. 136) with a = b = 8.5337(2) Å, c = 10.5595(5) Å, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) Å, b = 7.0724(7) Å, c = 10.080(1) Å, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) Å, b = 8.3282(2) Å, c = 13.0568(1) Å, beta = 102.940(2) degrees, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ(4))(2)](4)(-) (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe(4)](3)(-) units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS(4)](3)(-) tetrahedral groups to produce one-dimensional chains. The structures of V andVI feature the [P(2)Q(6)](4)(-) (Q = S, Se) group coordinated to the square planar Pd(2+) atoms, yielding [PdP(2)Q(6)](n)()(2)(n)()(-) chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.