Franck Millange

• Versailles Saint-Quentin-en-Yvelines University

The solvothermal synthesis of three new calcium-based metal-organic frameworks (MOFs) employing the tetratopic carboxylate ligand, 4,4',4'',4'''-(naphthalene-2,3,6,7-tetrayl)tetrabenzoate (NTTB) is reported. 1: Ca(H2NTTB)(DMA)2, 2: Ca5(H2NTTB)(NTTB)2(H2O)8 and 3: Ca5(H2NTTB)(NTTB)2(H2O)5 (DMA = N,N-dimethylacetamide). These...

Hybrid Metal Organic-Frameworks (MOF)/polymer materials have gathered many researcher’s consideration thanks to their varied functionalities and high processability. Herein, Metal Organic Frameworks (MOFs) have been successfully incorporated into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The s...

We present a review of the structural chemistry of metal‐organic framework materials with the MIL‐53 type structure. This family of materials is well‐known for its structural flexibility, and also the wide variety of metal cations and functional ligands that can be included. This gives rise to a set of multivariate materials and isoreticular analog...

A thiol-modified version of the porous metal organic framework MIL-53 is synthesised in a single step using the functionalised linker precursor 2,5-dithiol-1,4-benzenedicarboxylic acid and aluminium as the framework metal. Careful washing is needed to remove unreacted and dimerised linker from the material after synthesis, but once performed profil...

We review the various methods that have been used for the in situ study of the crystallization of metal–organic frameworks under real reaction conditions. This includes diffraction, small-angle scattering, and spectroscopic techniques under conventional solvothermal conditions and also more unusual synthesis methods, such as microwave, ultrasound,...

Using time-resolved monochromatic high energy X-ray diffraction, we present an in situ study of the solvothermal crystallisation of a new MOF [Yb2 (BDC)3 (DMF)2 ]⋅H2 O (BDC=benzene-1,4-dicarboxylate and DMF=N,N-dimethylformamide) under solvothermal conditions, from mixed water/DMF solvent. Analysis of high resolution powder patterns obtained reveal...

Using time-resolved monochromatic high energy X-ray diffraction, we present an in situ study of the solvothermal crystallisation of a new MOF [Yb2(BDC)3(DMF)2]⋅H2O (BDC=benzene-1,4-dicarboxylate and DMF=N,N-dimethylformamide) under solvothermal conditions, from mixed water/DMF solvent. Analysis of high resolution powder patterns obtained reveals an...

Two Co2+ metal-organic framework materials, constructed from a combination of 1,4-benzenedicarboxylate (BDC) and either 2,2′-dipyridyl-N-oxide (DPNO) or 2,2′-dipyridyl-N,N′-dioxide (DPNDO), are synthesized under solvothermal reaction conditions, and their structures solved by single crystal X-ray diffraction. Both have three-dimensional structures...

The interaction of CO2 with the porous metal-organic framework material MIL-53(Fe), FeIII(OH)0.8F0.2[O2C-C6H4-CO2] has been studied by complementary gas adsorption and high resolution powder X-ray diffraction as a function of gas pressure. It has been shown that CO2 adsorption occurs in three steps, with firstly the formation of an “Intermediate” (...

The complexes [Mo16O16S16(OH)16(abtc)(H2O)2]4− (1) and [Mo16O16S16(OH)16(abtc)2(H2O)2]8− (2) (abtc4− = 3,5-dicarboxyl-(3′,5′-dicarboxyazophenyl)benzene) have been obtained from the condensation of the [Mo2O2S2]2+ cluster in the presence of abtc4− ligand. Compounds 1 and 2 were characterized structurally, revealing host–guest architectures containin...

The synthesis and structures of metal-organic framework materials with three-dimensional structures related to the well-known MIL-53 framework are described. These have general chemical formula M(BDC)(PNO), where BDC = 1,4-benzenedicarboxylate, PNO = pyridine-N-oxide, and M = Mn, Co or Ni. The materials contain infinite chains of octahedral metal c...

In situ powder X-ray diffraction and thermogravimetry show that the iron(III) carboxylate material MIL-53(Fe) expands in two steps upon exposure to methanol vapour to give a ‘half open’ phase and then a fully expanded structure; these correspond to the uptake of one and two molar equivalents of methanol, respectively. This knowledge allows interpre...

We present new high-resolution inelastic neutron scattering (INS) spectra (measured using the TOSCA and MARI instruments at ISIS) and powder neutron diffraction data (measured on the diffractometer WISH at ISIS) from the interaction of the prototypical metal–organic framework HKUST-1 with various dosages of dihydrogen gas. The INS spectra show dire...

A time-resolved powder diffraction study of the crystallisation of porous metal organic framework materials with the CPO-27 structure ([M2(dhtp)(H2O)2]·8H2O where, dhtp=2,5-dioxoterephthalate) using the energy dispersive X-ray diffraction method is described. Crystallisation under solvothermal conditions is performed between 70 - 110 °C from clear...

Mixed-metal iron-vanadium analogues of the 1,4-benzenedicarboxylate (BDC) metal-organic framework MIL-53 have been synthesized solvothermally in N,N'-dimethylformamide (DMF) from metal chlorides using initial Fe:V ratios of 2:1 and 1:1. At 200 °C and short reaction time (1 h), materials (Fe,V)(II/III)BDC(DMF1-xFx) crystallize directly, whereas the...

Rare-earth layered hydroxides with intercalated tetrasulfonated porphyrins and corresponding to the chemical formula Ln(OH)(Por)·2HO (Ln = Eu, Tb; Por = 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and PdTPPS) have been prepared to investigate their photophysical properties. A slight variation of the synthetic procedure led to the metal-o...

The solvothermal synthesis of a novel mixed-s-block metal-organic framework is described, with crystallization brought about by use of the sodium salt of the benzo-(1,2;3,4;5,6)-tris(thiophene-2'-carboxylate) linker in combination with a lithium salt. The structure of the material was determined by single-crystal X-ray diffraction, which reveals an...

The adsorption of N/S-containing heterocyclic organic molecules in the flexible iron(iii) terephthalate MIL-53, Fe(III)(OH)(0.6)F(0.4)(O(2)C-C(6)H(4)-CO(2))·(H(2)O), from the liquid phase was studied with in situ energy dispersive X-ray diffraction (EDXRD), in order to follow the adsorption-induced expansion of the structure. For comparison with th...

The synthesis and characterisation of a three-dimensional lithium–organic framework MIL-145 is described, which upon thermal treatment yields a second open framework, MIL-146, that contains four and three-coordinate lithium centres: the coordinatively unsaturated trigonal planar lithium centres are able to reversibly bind water with crystallinity m...

The solvothermal reaction of cobalt chloride and 4,4′,4″-nitrilotrisbenzoic acid (H3NTB) in N,N′-dimethylformamide (DMF) affords a new three-dimensional Co-NTB compound with an empirical formula of HDMA2[Co5(NTB)4(H2O)3(DMA)]·7DMF (HDMA+, dimethylammonium). Its anionic network is built up from two connected NbO subnets and presents large hexagonal...

We report a study of the use of the porous metal–organic framework material MIL-53(Fe), FeIII(OH)0.8F0.2[O2C–C6H4–CO2], for the separation of BTEX mixtures (benzene, toluene, ethylbenzene, and the three xylene isomers). Crystal structures of the three host:guest materials MIL-53(Fe)[xylene], where xylene = the ortho, meta, or para isomer of dimethy...

A layered lithium carboxylate, Li4[C4H2S(CO2)2]2[C3H7NO]2, crystallizes under solvothermal conditions (160–180 °C) from lithium nitrate and the ligand 2,5-thiophenedicarboxylate in N,N-dimethylformamide as solvent. Single-crystal X-ray diffraction (Pbca a = 10.0216(18) Å, b = 18.327(4) Å, c = 24.871(5) Å) shows that the material is constructed from...

A comprehensive, time-resolved, energy-dispersive X-ray diffraction study of the uptake of liquid alcohols (methanol, ethanol, propan-1-ol and propan-2-ol) by the flexible metal-organic framework solid MIL-53(Fe)[H(2)O] is reported. In the case of the primary alcohols, a fluorinated version of the MIL-53(Fe) host (C2/c symmetry V ca. 1000 Å(3)), in...

An in situ, time-resolved energy dispersive powder X-ray diffraction study of the solvothermal crystallisation of the copper(II) 4,4',4 ''-benzene-1,3,5-triyl-tris(benzoate) metal-organic framework MOF-14 shows how reaction conditions must be carefully chosen to allow successful preparation of the material, since on prolonged heating at >= 120 degr...

The hydrolysis of the DMF solvent (DMF = N,N'-dimethylformamide) generates in situ the template cations DMA(+) (dimethylammonium cation): it leads to the first MOF type solid Fe(III)(0.5)Fe(II)(0.5)(OH,F)(O(2)C-C(6)H(4)-CO(2))·0.5DMA with a regular charge order Fe(III)/Fe(II) and an anionic framework with pores filled by counter-cations which behav...

The flexible metal-organic framework MIL-53(Cr) undergoes a dramatic volume expansion upon immersion in water at room temperature to form a crystalline hydrate in which water is held as a hydrogen-bonded tube: the hydration is readily reversible under ambient conditions as shown by time-resolved powder X-ray diffraction.

The field of "Metal-Organic Frameworks" (MOFs) has grown exponentially, giving rise to nanoporous materials with promising applications in gas storage, molecular separation or catalysis. Despite the use of solvothermal synthesis, some MOFs can be obtained only as polycrystalline samples and in those cases, powder diffraction is essential to charact...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The structures of four iron(III) carboxylate materials with the MIL-53 structure and the guest molecules water, pyridine, or 2,6-dimethylpyridine (2,6-lutidine) have been solved and refined from high-resolution powder X-ray diffraction data. These materials have porous structures constructed from infinite chains of trans-corner-shared {FeO(4)(OH,F)...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The one-dimensional gallium fluorophosphate Ga(HPO4)2F·H3N(CH2) 3NH3·2H2O 1 crystallises at room temperature from an aqueous mixture of Ga2O3, H3PO4, 1,3-diaminopropane, and HF; compound 1 converts to the three-dimensional microporous fluorophosphate ULM-3 on heating to 160 °C under hydrothermal conditions.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The optical properties of two-dimensional lanthanide dicarboxylates EuBDC or Eu2(H2O)2(O2C–C6H4–CO2)3 and EuCDC (denoted also MIL94) or Eu2(H2O)4(O2C–C6H10–CO2)3.2H2O are reported. The structures are built up from dimers of corner-sharing polyhedra and 1,3-benzenedicarboxylate (BDC) for EuBDC and from dimers of edge-sharing polyhedra and 1,3-benzen...

Journal article

X-ray absorption fine structure (XAFS) analysis of the Fe K-edge during lithium insertion and extraction into the metal organic framework material MIL-53 (FeIII(OH, F)bdc; bdc = benzene-1,4-dicarboxylate) reveals changes in local atomic environment about iron during the process. The average oxidation state of iron is reduced upon lithium insertion,...

(Graph Presented) Hydrogen sulfide gravimetric isotherm adsorption measurements were carried out on MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal-organic frameworks (MOFs). A two-step adsorption mechanism related to a breathing effect was observed for MIL-53 terephthalate-based MOFs. Methane adsorption measurements highlighted t...

Among the metal-organic frameworks (MOFs), MIL-53(Fe) or FeIII(OH)0.8F0.2[O2C−C6H4−CO2] was the first ever reported member to reversibly insert Li+ electrochemically. A variety of electroactive sorbents has been investigated in an attempt to increase its electrochemical capacity vs Li+/Li0. Here, we describe the synthesis and characterization of a...

The thermal behaviour of the nanoporous iron(iii) terephthalate MIL-53 is in stark contrast to its chromium and aluminium analogues which show an expansion of the cell during dehydration; with iron, reversible dehydration occurs via evolution of the structure through a highly distorted metastable anhydrous phase to a more regular phase above 423 K...

Breathing space: Time-resolved diffraction studies of the breathing of metal-organic frameworks in the presence of liquids reveal rapid exchange of one guest molecule by another. In some cases this occurs by direct exchange (as shown for water by pyridine), in others with the transient appearance of crystalline intermediates corresponding to partia...

In this paper the preparation of Metal Organic Frameworks with Cr and Al metals is described and their sorption capabilities are evaluated in the case of the n-alkanes adsorbed at ambient temperatures. The adsorption isotherms obtained strongly suggest a breathing mechanism of the frameworks leading to unprecedented sorption volumes. In terms of ad...

We demonstrate here the reversible electrochemical insertion of lithium into the hybrid porous solid FeIII(OH)0.8F0.2[O2C-C6H4-CO2]. Used as an electrode in Li-half cell, this material shows a reversible redox process around 3.0V vs. Li+/Li° exchanging 0.6Li per formula unit with interesting capacity retention and rate capability. Moreover, it reve...

Metal−organic frameworks (MOFs) synthesized in a building-block approach from organic linkers and metal corner units offer the opportunity to design materials with high surface areas for adsorption applications by assembling the appropriate building blocks. In this paper, we show that the surface area calculated in a geometric fashion from the crys...

Organic–inorganic hybrid materials with open-framework structure are currently studied since they represent a class of materials with a great potential as luminescent materials for photonic applications. In this aim, optical properties of Eu3+ in a hybrid material Ln((C6H3)–CO2)3) (Ln∼Y, Eu, Gd) has been investigated. Its three-dimensional structur...

Lithiumbatterien: Als Elektrode in einer Lithium-Halbzelle zeigt das metall-organische Gerüst [LixFeIIxFeIII1−x(OH)0.8F0.2L] (L=O2CC6H4CO2) einen reversiblen Redoxprozess bei etwa 3.0 V gegen Li+/Li0, der durch eine interessante Kapazitätsretention und Strombelastbarkeit gekennzeichnet ist (siehe Spannungsprofil einer [LixFe(OH)0.8F0.2L]-Halbzelle;...

There's more to LiFe: When used as an electrode in a lithium half cell, the metal-organic framework [LixFeIIxFe III1-x(OH)0.8-F0.2L] (L = O 2CC6H4CO2) shows a reversible redox process around 3.0 V versus Li+/ Li0 with interesting capacity retention and rate capability (see voltage profile for a [Li xFe(OH)0.8F0.2L] half cell; inset: representation...

The new rare-earth dicarboxylate solid Eu2(H2O)4{C6H10–(CO2)2}3·2H2O or MIL-94 has been isolated under hydrothermal conditions. Its layered structure, which was solved using X-ray powder diffraction data, is built up from dimers of nine-coordinated edge-sharing polyhedra linked through 1,3-cyclohexane dicarboxylate (1,3-CHC) moieties. A comparative...

We demonstrate here the reversible electrochemical insertion of lithium into the hybrid porous solid FeIII(OH)0.8F0.2[O2C-C6H4-CO2]. Used as an electrode in Li-half cell, this material shows a reversible redox process around 3.0V vs. Li+/Li° exchanging 0.6Li per formula unit with interesting capacity retention and rate capability. Moreover, it reve...

A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.5.6H2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO3)3.9H2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the con...

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr{sup III}(OH).{l_brace}O{sub 2}C-C{sub 6}(CH{sub 3}){sub 4}-CO{sub 2}{r_brace}.nH{sub 2}O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate comp...

EXAFS data measured from amorphous intermediates and crystallisation solutions provides the first evidence that trimeric iron oxide secondary building units remain intact during crystallisation of the metal-organic framework MIL-89 from starting materials to products.

A study of the zeotypic giant pores chromium(III) tricarboxylate Cr(III)3OF(x)(OH)(1-x)(H2O)2 x {C6H3-(CO2)3}2 x nH2O (MIL-100) has been performed. First, its thermal behavior, studied by X-ray thermodiffractometry and infrared spectroscopy, indicates that the departure of water occurs without any pore contraction and no loss in crystallinity, whic...

A new three-dimensional lanthanide(III) tricarboxylate, MIL-811 or Pr(III)(H2O)(C6H3 2 3 MIL-81ht (III) 6 3 2 3 Crystal data for MIL-81: monoclinic space group P21P21 with a=10.272(1) Åa=10.272(1) Å, b=7.057(1) Åb=7.057(1) Å, c=6.232(1) Åc=6.232(1) Å, β=93.668(4)°β=93.668(4)° and Z=2Z=2. Crystal data for MIL-81ht: triclinic space group P-1 with a...

We report here a new family of isoreticular MOFs, comprising three larger analogues of the nanoporous metallocarboxylate MIL-88; these solids were synthesized using a controlled SBU approach and the three crystal structures were solved using an original simulation-assisted structure determination method in direct space.

The first direct imaging of giant pores of the metal-organic framework MIL-101 was discussed. The structure of MIL-101 was built up from a corner-sharing of so-called supertetrahedra (ST), which is made from the linkage of inorganic trimers and 1,4-benzene dicarboxylate (1,4-BDC) anions. The connection of ST ensures a three-dimensional network of c...

A distinct step in the isotherm occurs during the adsorption of CO2 on MIL-53 at 304 K. Such behavior is neither observed during the adsorption of CH4 on MIL-53 nor during the adsorption on the isostructural MIL-47. This phenomenon seems to be due to a different mechanism than that of previous adsorption steps on MOF samples. It is suggested that a...

We combined targeted chemistry and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, withverylargeporesizes and surface area. Its zeotype cubic structure has a giant cell volume (∼702,000 cubic angstroms), a hierarchy of extra-large pore sizes (∼30 to 34 angstroms), and a Langmuir surface area for N2 of...

A new three-dimensional europium-doped Yttrium(III) tricarboxylate, MIL-92LT1 or Y1−xEux(H2O)2{C6H3(CO2)3} (x∼0.03) (LT: Low Temperature) has been synthesised hydrothermally. Its three-dimensional structure, determined using X-ray powder diffraction data, is built-up from isolated eight coordinated Ln(III) monocapped square antiprisms (Ln=Y, Eu) li...

In the domain of porous solids with inorganic or hybrid frameworks, the combination of mastered chemistry and of computer simulations pushes forward the limits of the classical approach and allows the full determination from powder diffraction data of architectures with cells of several hundred thousand cubic angstroms with hierarchies of giant por...

We present results of the first systematic study of the hydrothermal synthesis of the manganites La0.5M0.5MnO3 (M = Ca, Sr, Ba), and a detailed characterisation of the products using a number of experimental methods. All three materials can be produced as phase-pure, polycrystalline powders in one step from solutions of metal salts in aqueous potas...

The hydrothermal synthesis of the aluminum phosphate Na2Al7(PO4)12·4trenH3·Na(H2O)16 (MIL-74) has been studied by X-ray diffraction (conventional source) and in-situ time-resolved energy-dispersive X-ray diffraction (synchrotron radiation). Before the crystallization of MIL-74, the reaction of the starting aqueous aluminophosphate gel containing th...

Eine perfekte Kombination: Ein trimerer CrIII-Baustein und 1,3,5-Benzoltricarboxylat führen zum pulverförmigen Feststoff MIL-100. Simulationen ergaben eine mögliche Kristallstruktur, die in Einklang mit dem Pulverdiffraktogramm ist. Diese einzigartige Kombination aus Simulation und Diffraktometrie ermöglichte die Strukturbestimmung eines zeolithart...

Fertigbauweise: Eine Solvothermalsynthese mit trimeren sekundären Baueinheiten führte zu zwei neuen Eisen(III)-dicarboxylaten mit offenen Gerüststrukturen, die durch Röntgenpulverbeugung charakterisiert wurden. In den 3D-Netzwerken wirken die Dicarboxylate als Brücken zwischen den Trieisen-Einheiten. Die 1D-Poren dieser kationischen Netze (siehe Bi...

Two new organically templated zinc selenites MIL-86 or [H 2N(CH2)2NH2]2·Zn4(SeO3)4 and MIL-87 or [H 3N(CH2)3NH3]4·Zn4(SeO3)8 have been prepared by the reaction of ZnO with SeO2 under hydrothermal conditions in the presence of organic amines. Crystal data: MIL-86, monoclinic, space group P21/n, a=6.7712(4) Å, b=9.4520(5) Å, c=8.0295(4) Å, β=113.601(...

A new three-dimensional iron(III) dicarboxylate, MIL-85 or FeIII2O{O2C−CH3}2{O2C−C6H4−CO2}·2CH3OH, has been obtained under solvothermal conditions, and its structure was determined using X-ray powder diffraction data. Its chiral framework is built up from helical chains of iron(III) octahedra linked through terephthalate dianions. This creates a th...

A new three-dimensional europium-doped yttrium 1,3,5-benzenetricarboxylate has been obtained under hydrothermal conditions. The structure of MIL-78(Y, Eu) or Y1−xEux((C6H3)–(CO2)3) (x 0.024) has been solved from X-ray powder diffraction data (a = 6.941(1) Å, b = 14.700(2) Å, c = 8.488(1) Å, β = 107.73(1)°, V = 824.9(4) Å3, space group C2/m (no. 12)...

A new three-dimensional rare-earth() dicarboxylate, (Eu) or Eu(OC-CH-CO), has been obtained under hydrothermal conditions from aqueous mixtures of europium nitrate and 1,3-adamantanedicarboxylic acid. Its three-dimensional structure consists of chains built up from face-sharing nine-coordinated rare-earth() polyhedra connected by the 1,3-adamantane...

Two new organically templated zinc selenites MIL-86 or [H2N(CH2)2NH2]2·Zn4(SeO3)4 and MIL-87 or [H3N(CH2)3NH3]4·Zn4(SeO3)8 have been prepared by the reaction of ZnO with SeO2 under hydrothermal conditions in the presence of organic amines. Crystal data: MIL-86, monoclinic, space group P21/n, a=6.7712(4) Å, b=9.4520(5) Å, c=8.0295(4) Å, β=113.601(1)...

Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+); these solids show a hydrogen storage capacity of 3.8 and 3.1 wt.% respectively when loaded at 77 K under 1.6 MPa.

An iron−aluminum phosphate Fe3Al6(PO4)12·4tren·17H2O (MIL-74) has been hydrothermally synthesized with the tris(2-aminoethyl)amine (tren) as a structure-directing agent (453 K, 36 h, autogenous pressure). Single-crystal X-ray diffraction, magnetic measurements, and Mössbauer and solid-state NMR spectroscopies were carried out to characterize the co...

A new type of three-dimensional vanadium(III) dicarboxylate, MIL-71 or VIII2(OH)2F2{O2C-C6H4-CO2}·H2O, has been obtained under hydrothermal conditions from aqueous mixtures of vanadium, 1,4-benzenedicarboxylic acid, and HF. MIL-71cal or VIV2O2F2{O2C-C6H4-CO2} is obtained by calcination of the parent compound in air at 250 °C. The three-dimensional...

The nuclear and magnetic structures of the colossal magnetoresistive compounds Nd0.7Ba0.3−ySryMnO3 (0⩽y⩽0.2) have been investigated by means of neutron powder diffraction. For all the Ba/Sr substitutions, the nuclear structure remains orthorhombic within temperature range 1.5–293 K. However, the compound Nd0.7Ba0.3MnO3 is characterized by the cryst...

For Abstract see ChemInform Abstract in Full Text.

For Abstract see ChemInform Abstract in Full Text.

For Abstract see ChemInform Abstract in Full Text.

The first three-dimensional chromium(III) dicarboxylate, MIL-53as or Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)].[HO(2)C-C(6)H(4)-CO(2)H](0.75), has been obtained under hydrothermal conditions (as: as-synthesized). The free acid can be removed by calcination giving the resulting solid, MIL-53ht or Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)]. At room temperature,...

The first three-dimensional chromium(III) dicarboxylate, MIL-53as or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}0.75, has been obtained under hydrothermal conditions (as: as-synthesized). The free acid can be removed by calcination giving the resulting solid, MIL-53ht or CrIII(OH)·{O2C−C6H4−CO2}. At room temperature, MIL-53ht adsorbs atmospheric wate...

The Dion-Jacobson-type layered perovskite, RbCa2Nb3O10, has been prepared by two different synthetic routes at the moderate temperature of 800 degreesC. With a new molten salt approach, combining a 1:4:3 molar ratio of K2CO3:CaCO3:Nb2O5 with a large excess of RbCl leads to the rapid formation of RbCa2Nb3O10 at 800 degreesC. Although the product inc...

Two one-dimensional gallium fluorodiphosphates Ga(P2O7)F·H3N(CH2)3NH3·3H2O, 1, and Ga(P2O7)F·H3N(CH2)3NH3·H2O, 2, have been synthesized under mild conditions (<100 °C) from aqueous mixtures of Ga(NO3)3·6H2O, P2O5, 1,3-diaminopropane, and HF. Their structures consist of anionic chains of formula Ga(P2O7)F2- containing corner-sharing {GaO4F2} octahed...

LiGaPO4(OH) and LiGaPO4F1−δ (OH)δ (δ≈0.26) were hydrothermally synthesized at 180°C for 36 hours. Both compounds were analogous to the lithium aluminophosphates belonging to the minerals series of montebrasite (pure OH form) and amblygonite (mixed OH,F form). The solids crystallize in the triclinic cell (P1̄) with a=7.1487(2), b=5.3005(2), c=5.0877...

The first three-dimensional chromium(III) dicarboxylate compounds have been isolated and their structures solved from powder X-ray diffraction data; the flexible framework of these materials delimits large pores.

Two novel gallium fluorodiphosphates have been isolated and their structures solved ab initio from powder X-ray diffraction data; the materials readily interconvert under hydrothermal conditions, and are metastable with respect to an open-framework zeolitic gallium fluorophosphate, during the synthesis of which they are present as transient interme...

Three-dimensional europium terephthalates have been obtained under hydrothermal conditions and their structures solved using either X-ray powder diffraction or single-crystal data. MIL-51LT or Eu2III(H2O)2(OH)4(O2C−C6H4−CO2) and MIL-51HT or Eu2III(OH)4(O2C−C6H4−CO2) contain only trivalent europium, while MIL-52 or EuII(O2C−C6H4−CO2) involves only e...

DOI:https://doi.org/10.1103/PhysRevB.65.109901

The hydrothermal crystallization of barium titanate, BaTiO3, has been studied in situ by time-resolved powder neutron diffraction methods using the recently developed Oxford/ISIS hydrothermal cell. This technique has allowed the formation of the ferroelectric ceramic to be followed in a noninvasive manner in real time and under genuine reaction con...

We report the first example of selective intercalation of nucleoside monophosphates in a layered host material. The intercalated nucleoside monophosphates can then be quantitatively recovered from the inorganic host and so this opens up the possibility of using simple layered inorganic hosts as rapid, cost effective and recyclable materials for the...

The role played by the Nd ions in the magnetic properties of Nd0.5Ca0.5MnO3 and Nd0.7Ca0.3MnO3 is studied using static magnetization, neutron diffraction, and high frequency (9.4-475 GHz) electron spin resonance (ESR). We show that the Nd ions are weakly coupled to the Mn ions via ferromagnetic exchange and are responsible for the peculiar ferromag...

The role played by the Nd ions in the magnetic properties of Nd0.5Ca0.5MnO3 and Nd0.7Ca0.3MnO3 is studied using static magnetization, neutron diffraction and high frequency (9.4-475GHz) Electron Spin Resonance. We show that the Nd ions are weakly coupled to the Mn ions via ferromagnetic exchange and are responsible for the peculiar ferromagnetic re...

The layered gallium fluorophosphate Ga3F2(OH)4(H2- PO4)(HPO4)3 [H3N(CH2)6NH3]2 ·3.5H2O (1) crystallises at room temperature from the supernatant liquid taken during the hydrothermal synthesis of the large-pore material ULM-5; the phase has a topology not previously seen among the Group 13 phosphates.

In Nd0.5Ca0.5Mn0.3, Mn3+ and Mn4+ ions become ordered below T-co = 250 K. At 160 K, a long-range antiferromagnetic order is established. The ESR spectra have revealed that, for T-N < T < T-CO, this phase is non magnetic but presents strong antiferromagnetic fluctuations. No evidence of a separated ferromagnetic phase was detected in this temperatur...

The hydrothermal crystallization of sodium zeolite A from amorphous aluminosilicate gels at 80-120 degreesC has been studied by time-resolved in situ energy-dispersive X-ray diffraction. This has allowed the course of crystallization to be followed in greater detail than previously possible. Quantitative crystallization curves have been obtained, a...

20-ring windows are present in a large-pore gallium fluorophosphate (see picture) that can be crystallized at 50°C. This offers the possibility of discovering new zeolitic phases. The phosphate material may be rendered microporous by thermal treatment.

20-gliedrige Ringe bilden großporige Fenster in einem Galliumfluorphosphat (siehe Bild), das bei 50°C zur Kristallisation gebracht werden kann. Mit diesen milden experimentellen Bedingungen sollte die Entdeckung neuer, mikroporöser Zeolithphasen möglich sein.

The design, construction, and use of a furnace from which time-resolved x-ray diffraction data may be measured from reacting mixtures of solids or of solids and liquids is described. The furnace is a vertical tube design, constructed from commercially available components, and can operate at temperatures of up to 1000 °C. The apparatus is designed...