Layered Monophosphate Tungsten Bronzes [Ba(PO4 )2 ]Wm O3m-3 : 2D Metals with Locked Charge-Density-Wave Instabilities.

Phosphate tungsten and molybenum bronzes represent an outstanding class of materials displaying textbook examples of charge-density-wave (CDW) physics among other fundamental properties. Here we report on the existence of a novel structural branch with the general formula [Ba(PO4 )2 ][Wm O3m-3 ] (m=3, 4 and 5) denominated 'layered monophosphate tungsten bronzes' (L-MPTB). It results from thick [Ba(PO4 )2 ]4- spacer layers disrupting the cationic metal-oxide 2D units and enforcing an overall trigonal structure. Their symmetries are preserved down to 1.8 K and the compounds show metallic behaviour with no clear anomaly as a function of temperature. However, their electronic structure displays the characteristic Fermi surface of previous bronzes derived from 5d W states with hidden nesting properties. By analogy with previous bronzes, such a Fermi surface should result into CDW order. Evidence of CDW order was only indirectly observed in the low-temperature specific heat, giving an exotic context at the crossover between stable 2D metals and CDW order.

An investigation on fatigue, fracture resistance, and color properties of aesthetic CAD/CAM monolithic ceramics.

OBJECTIVES: To evaluate and compare fracture resistance, translucency, and color reproducibility, as well as the effect of aging on the fracture load and color stability of novel monolithic CAD/CAM ceramics. MATERIALS AND METHODS: One hundred crowns of uniform thickness were milled from five ceramic blocks (n = 20): partially crystallized lithium disilicate (PLD) and fully crystallized lithium disilicate (FLD), lithium metasilicate (LMS), 4Y-TZP (SMZ), and 5Y-TZP (UMZ) monolithic zirconia. PLD crowns were glazed, LMS was fired, and FLD was polished. SMZ and UMZ crowns were sintered and polished. Crowns were adhesively cemented to epoxy dies. Half of the crowns (n = 10) were subjected to 1.200.000 load cycles with thermal cycling. Color space values L, a, b defined by the Commission Internationale de l´Eclairage (CIELAB) were measured before and after aging, and (∆E) was calculated. Both aged and non-aged specimens were loaded until fracture in a universal testing machine and the fracture load was recorded. X-ray diffraction (XRD) and scanning electron microscope (SEM) fractographic analysis were carried out on fractured fragments of representative samples. For translucency and color reproducibility, 50 rectangular-shaped specimens were fabricated and processed as described previously. Color values were measured over black and white backgrounds, and the translucency parameter (TP) was computed. Using the shade verification mode, (∆E) to shade A3 was calculated. Data were statistically analyzed using one-way and two-way ANOVA, and t-test. RESULTS: Aging did not affect fracture resistance significantly (p > 0.05). The highest mean fracture load was obtained for the SMZ and UMZ. A significant color change was observed after aging in all groups. The highest TP was noted for FLD. SMZ and UMZ had the best shade match. CONCLUSIONS: Zirconia showed higher fracture resistance and color stability than lithium silicate ceramics. Lithium silicate ceramics were more translucent. The experimental FLD demonstrated high translucency. CLINICAL RELEVANCE: Tested ceramics showed sufficient stability to withstand masticatory forces. Characterization of final restorations might be mandatory for better color match.

Kinetically Controlled Reduction of ß-Vanadyl(V) Orthophosphate: Synthesis and Characterization of New Metastable Polymorphs of Vanadium(III) Phosphate.

Two thermodynamically metastable polymorphs of vanadium(III) phosphate, VIIIPO4-m1 and VPO4-m2, have been obtained via reduction of ß-VVOPO4 by moist hydrogen. The XRPD pattern of VPO4-m1 can be assigned based on the crystal structure of ß-VVOPO4, though with distinctly different lattice parameters (VPO4-m1/ß-VOPO4: Pnma, a = 7.3453(12)/7.7863(5) Å, b = 6.4001(12)/6.1329(3) Å, c = 7.3196(13)/6.9673(5) Å). The XRPD pattern of VPO4-m2 was found to be very similar to that of Fe2(VO)(P2O7)(PO4) (VPO4-m2: P21/m, Z = 2, a = 8.792(4) Å, b = 5.269(2) Å, c = 10.398(6) Å, ß = 112.60(4)°). The crystal structure models for VPO4-m1 and VPO4-m2 have been optimized by DFT calculations. Polymorph m1 contains the unprecedented butterfly shaped [VIIIO4] chromophore and has been further characterized by magnetic measurements, by powder reflectance spectroscopy (NIR/vis/UV), and IR spectroscopy. For six polymorphic forms of VPO4 (m1', m1'', m2, m3, m4, and m5), DFT calculations have been performed. For the existence of VPO4-m1', -m1'', and -m2, our experiments provide evidence. VPO4-m3, -m4, and -m5 were obtained by structure optimization based on reduced ß-VOPO4. Their stability is predicted by the DFT calculations.

Synthesis-Controlled Polymorphism and Optical Properties of Phyllosilicate-Analogous Borosulfates M[B2 (SO4 )4 ] (M=Mg, Co).

Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate-analogous borosulfates is unraveled by adjusting the oleum (65 % SO3 ) content. The new polymorphs ß-Mg[B2 (SO4 )4 ] and α-Co[B2 (SO4 )4 ] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The α-modification comprises cations between the layers, whereas in the ß-modification cations are embedded within the layers. With this new synthetic approach, phase-pure compounds of the respective polymorphs α-Mg[B2 (SO4 )4 ] and ß-Co[B2 (SO4 )4 ] were also achieved. Tanabe-Sugano analysis of the Co2+ polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two-dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single-crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations.

Electronic origin of negative thermal expansion in V2OPO4.

Negative volume expansion between 620 and 800 K in V2OPO4 is discovered to be of electronic origin due to the charge ordering transition at 605 K. Domain reorientation and coexistence of the low and high temperature phases close to the transition are observed in X-ray diffraction data from single crystals grown by chemical vapour transport.

Open-Shell 3d Transition Metal Nitridophosphates MII P8 N14 (MII =Fe, Co, Ni) by High-Pressure Metathesis.

3d transition metal nitridophosphates MII P8 N14 (MII =Fe, Co, Ni) were prepared by high-pressure metathesis indicating that this route might give a systematic access to a structurally rich family of M-P-N compounds. Their structures, which are stable in air up to at least 1273 K, were determined through powder X-ray diffraction and consist of highly condensed tetra-layers of PN4 tetrahedra and MN6 octahedra. Magnetic measurements revealed paramagnetic behavior of CoP8 N14 and NiP8 N14 down to low temperatures while, FeP8 N14 exhibits an antiferromagnetic transition at TN =3.5(1) K. Curie-Weiss fits of the paramagnetic regime indicate that the transition metal cations are in a oxidation state +II, which was corroborated by Mössbauer spectroscopy for FeP8 N14 . The ligand field exerted by the nitride ions in CoP8 N14 and NiP8 N14 was determined from UV/Vis/NIR data and is comparable to that of aqua-ligands and oxophosphates.

Mechanochemical dehydrocoupling of dimethylamine borane and hydrogenation reactions using Wilkinson's catalyst.

Mechanochemistry enabled the selective synthesis of the recherché orange polymorph of Wilkinson's catalyst [RhCl(PPh3)3]. The mechanochemically prepared Rh-complex catalysed the solvent-free dehydrogenation of Me2NH·BH3 in a ball mill. The in situ-generated hydrogen (H2) could be utilised for Rh-catalysed hydrogenation reactions by ball milling.

BonnMag: Computer program for ligand-field analysis of f n systems within the angular overlap model.

The program BonnMag has been developed to calculate the absorption spectra and temperature dependent magnetic susceptibilities of f n systems. The computations of the transition energies are performed within the angular overlap model. Using Judd-Ofelt theory BonnMag allows estimation of the relative absorption coefficients of the electronic transitions with reasonable accuracy. A description of the theoretical background of the implemented methods is given. Using Slater-Condon-Shortley parameters and spin-orbit coupling coefficients for free Ln3+ ions from ab initio calculations, the transition energies of all Ln3+ ions are calculated and compared to the results from CASSCF/NEV-PT2 calculations. Splitting due to the ligand field as well as transition energies of all Cs2 NaLnCl6 (except Gd and Pm) are calculated using parameters reported in the literature. Based on the comparison between theory and experiment, the potential and limitations of the program BonnMag are shown. © 2017 Wiley Periodicals, Inc.

Optical Spectra and Magnetic Behavior of a Wide Range of Europium(III) Oxo-Compounds: Analysis of the Ligand-Field Effects.

The europium-oxygen interaction in nine different europium(III) oxo-compounds (including C-type Eu2O3) was investigated on the basis of powder reflectance spectra (near-IR/vis/UV) and temperature-dependent magnetic measurements. Computation of the transition energies and of the effective Bohr magneton numbers for Eu3+ in the different ligand fields were performed within the framework of the angular overlap model (AOM) using the computer program BonnMag. These calculations show that all electronic transition energies in the optical spectra, the magnetic susceptibilities as well as their temperature dependence, are very well-accounted for by AOM. BonnMag provides a facile way to perform these calculations. Analysis of the obtained "best fit" AOM parameters eσ(EuIII-O) shows that these are significantly influenced by the further bonding partners of oxygen ("second-sphere ligand-field effect"). An increase of eσ, max(EuIII-O) from 404 cm-1 (EuPO4) to 687 cm-1 (EuSbO4), both normalized to d(EuIII-O) = 2.38 Å, is found. Correlation of this variation to oxide polarizability and optical basicity of the oxo-compounds is discussed.

Synthesis and Characterization of the High-Pressure Nickel Borate γ-NiB4O7.

γ-NiB4O7 was synthesized in a high-pressure/high-temperature experiment at 5 GPa and 900 °C. The single-crystal structure analysis yielded the following results: space group P6522 (No. 179), a = 425.6(2), c = 3490.5(2) pm, V = 0.5475(2) nm3, Z = 6, and Flack parameter x = -0.010(5). Second harmonic generation measurements confirmed the acentric crystal structure. Furthermore, γ-NiB4O7 was characterized via vibrational as well as single-crystal electronic absorption spectroscopy, magnetic measurements, high-temperature X-ray diffraction, differential scanning calorimetry, and thermogravimetry. Density functional theory-based calculations were performed to facilitate band assignments to vibrational modes and to evaluate the elastic properties and phase stability of γ-NiB4O7.

High-Pressure Phase Transformations in TiPO4 : A Route to Pentacoordinated Phosphorus.

Titanium(III) phosphate, TiPO4 , is a typical example of an oxyphosphorus compound containing covalent P-O bonds. Single-crystal X-ray diffraction studies of TiPO4 reveal complex and unexpected structural and chemical behavior as a function of pressure at room temperature. A series of phase transitions lead to the high-pressure phase V, which is stable above 46 GPa and features an unusual oxygen coordination of the phosphorus atoms. TiPO4 -V is the first inorganic phosphorus-containing compound that exhibits fivefold coordination with oxygen. Up to the highest studied pressure of 56 GPa, TiPO4 -V coexists with TiPO4 -IV, which is less dense and might be kinetically stabilized. Above a pressure of about 6 GPa, TiPO4 -II is found to be an incommensurately modulated phase whereas a lock-in transition at about 7 GPa leads to TiPO4 -III with a fourfold superstructure compared to the structure of TiPO4 -I at ambient conditions. TiPO4 -II and TiPO4 -III are similar to the corresponding low-temperature incommensurate and commensurate magnetic phases and reflect the strong pressure dependence of the spin-Peierls interactions.

The Electronic States of U(4+) in U(PO4)Cl: An Example for Angular Overlap Modeling of 5f(n) Systems.

Detailed experimental data on UPO4Cl comprising single-crystal UV/vis/NIR spectra and temperature-dependent magnetic susceptibilities form the basis for the investigation of the electronic structure of the U(4+) cation in UPO4Cl. For modeling of the observed physical properties the angular overlap model (AOM) was successfully employed. The computations were performed using the newly developed computer program BonnMag. The calculations show that all electronic transitions and the magnetic susceptibility as well as its temperature dependence are well-reproduced within the AOM framework. Using Judd-Ofelt theory BonnMag allows estimation of the relative absorption coefficients of the electronic transitions with reasonable accuracy. Ligand field splitting for states originating from f-electron configurations are determined. Slater-Condon-Shortley parameters and the spin-orbit coupling constant for U(4+) were taken from literature. The good transferability of AOM parameters for U(4+) is confirmed by calculations of the absorption spectra of UP2O7 and (U2O)(PO4)2. The effect of variation of the fit parameters is investigated. AOM parameters for U(4+) (5f) are compared to those of the rare-earth elements (4f) and transition metals (3d).

Comprehensive Characterization of the Electronic Structure of U(4+) in Uranium(IV) Phosphate Chloride.

Emerald-green single crystals of U(PO4)Cl were grown by chemical vapor transport in a temperature gradient (1000 → 900 °C). The crystal structure of U(PO4)Cl (Cmcm, Z = 4, a = 5.2289(7) Å, b = 11.709(2) Å, c = 6.9991(8) Å) consists of a three-dimensional network of [PO4] tetrahedra and bicapped octahedral [U(IV)O6Cl2] groups. Polarized absorption spectra measured for two perpendicular polarization directions show a large number of well-resolved electronic transitions. These transitions can be fully assigned on the basis of a detailed ligand-field treatment within the framework of the angular overlap model. The magnetic behavior predicted on the basis of the spectroscopic data is in agreement with an f (2) system and perfectly matched by the results of temperature-dependent susceptibility measurements.

Homonuclear Mixed-Valent Cobalt Imidazolate Framework for Oxygen-Evolution Electrocatalysis.

Herein, the synthesis and characterization of the first mixed-valent, purely cobalt-based zeolitic imidazolate framework, Co(II)3Co(III)2(C3H3N2)12 is presented. The material adopts the cubic garnet-type structure and combines high thermal stability of up to 350 °C with excellent chemical stability. Electrochemical characterization showed that the cobalt centres are redox active and efficiently support oxygen evolution, thus rendering this framework a potential candidate for single-site heterogeneous catalysis based on earth-abundant elements.

(Bis(terpyridine))copper(II) Tetraphenylborate: A Complex Example for the Jahn-Teller Effect.

The surprisingly complicated crystal structure of (bis(terpyridine))copper(II) tetraphenylborate [Cu(tpy)2](BPh4)2 (tpy = 2,2':6',2″-terpyridine) consists of six crystallographically independent [Cu(tpy)2](2+) complexes. At ambient temperature, five out of six [Cu(II)N6] chromophores appear to be compressed octahedra, while at 100 K, four exhibit elongated and only two compressed octahedral geometry. Temperature dependent single crystal UV/vis (100, 298 K) and EPR measurements (20, 100, 298 K) as well as AOM calculations suggest that the octahedra which show apparently compressed octahedral geometry (XRD) result from dynamic Jahn-Teller behavior of elongated octahedra [Cu(II)N6]. The detailed correlation of structural and spectroscopic data allows an understanding of the strongly solvent-dependent structures of the [Cu(tpy)2](2+) complex in solution.

Penta-cobalt(II) divanadium(III) tetrakis(diphosphate), Co5V2(P2O7)4.

Co5V2(P2O7)4 was crystallized by chemical vapour transport using HCl as transport agent. Its crystal structure is isotypic to that of Fe(II) 5Fe(III) 2(P2O7)4 and can be regarded as a member of the thortveitite structure family with corrugated layers of metal-oxygen polyhedra extending parallel to (010). Significant occupational disorder between cobalt(II) and vanadium(III) is observed. Four of the five cation sites are occupied by both cobalt and vanadium. The fifth cation site (Co1) is occupied by cobalt only. Sites Co1, M3 and M4 are located on twofold axes. Sites Co1, M2, M3 and M4 show o-cta-hedral coordination by oxygen; M5 has a square-pyramidal environment.

Ca3Sm3[Si9N17] and Ca3Yb3[Si9N17] nitridosilicates with interpenetrating nets that consist of star-shaped [N[4](SiN3)4] units and [Si5N16] supertetrahedra.

New nitridosilicates Ca(3)Sm(3)[Si(9)N(17)] and Ca(3)Yb(3)[Si(9)N(17)] were synthesized from the reactions of the pure metals (calcium and samarium/ytterbium) with silicon diimide "Si(NH)(2) " in a radio-frequency (rf) furnace at temperatures of up to 1650 °C. These isotypic compounds crystallize in the cubic space group P4(-)3m (no. 215) with lattice parameters a=739.50(3) pm; V=0.4044(1) nm(3); Z=1; wR(2) =0.029 (240 diffraction data, 26 parameters) for Ca(3)Sm(3)[Si(9)N(17)] and a=730.20(2) pm; V=0.3893(1) nm(3); wR(2) =0.039 (387 diffraction data, 27 parameters) for Ca(3)Yb(3)[Si(9)N(17)]. The new structure type of Ca(3)RE(3)[Si(9)N(17)] (RE=Sm, Yb) consists of two independent infinite networks, each of which have an expanded sphalerite (ZnS) topology in which the positions of the Zn and S atoms are replaced by voluminous [N([4])(SiN(3))(4)] units and [Si(5)N(16)] supertetrahedra, respectively, thereby displaying twofold interpenetration. As well, a structural description of Ca(3)Yb(3)[Si(9)N(17)], its thermal stability, and magnetic properties, as well as UV/Vis, IR, and Raman spectra, are presented.

Intermediate states on the way to edge-sharing BO4 tetrahedra in M6B22O39·H2O (M=Fe, Co).

The new borates Fe(II)(6)B(22)O(39)·H(2)O (colourless) and Co(II)(6)B(22)O(39)·H(2)O (dichroic: red/bluish) were synthesised under the high-pressure/high-temperature conditions of 6 GPa and 880 °C (Fe)/950 °C (Co) in a Walker-type multi-anvil apparatus. The compounds crystallise in the orthorhombic space group Pmn2(1) (Z=2) with the lattice parameters a=771.9(2), b=823.4(2), c=1768.0(4) pm, V=1.1237(4) nm(3), R(1)=0.0476, wR(2)=0.0902 (all data) for Fe(6)B(22)O(39)·H(2)O and a=770.1(2), b=817.6(2), c=1746.9(4) pm, V=1.0999(4) nm(3), R(1)=0.0513, wR(2)=0.0939 (all data) for Co(6)B(22)O(39)·H(2)O. The new structure type of M(6)B(22)O(39)·H(2)O (M=Fe, Co) is built up from corner-sharing BO(4) tetrahedra and BO(3) groups, the latter being distorted and close to BO(4) tetrahedra if additional oxygen atoms of the neighbouring BO(4) tetrahedra are considered in the coordination sphere. This situation can be regarded as an intermediate state in the formation of edge-sharing tetrahedra. The structure consists of corrugated multiple layers interconnected by BO(3)/BO(4) groups to form Z-shaped channels. Inside these channels, iron and cobalt show octahedral (M1, M3, M4, M5) and strongly distorted tetrahedral (M2, M6) coordination by oxygen atoms. Co(II)(6)B(22)O(39)·H(2)O is dichroic and the low symmetry of the chromophore [Co(II)O(4)] is reflected by the polarised absorption spectra (Δ(t)=4650 cm(-1), B=878 cm(-1)).

Synthesis, crystal structure and Raman spectrum of K(2)[(Pt(2))(HPO(4))(4)(H(2)O)(2)] containing (Pt(2)) ions.

In the crystal structure of the acid platinum phosphate dipotassium di-µ-hydrogenphosphato-bis-[aqua-platinum(III)](Pt-Pt), K(2)[Pt(2)(HPO(4))(4)(H(2)O)(2)], the (Pt(2))(6+) dumbbells within the paddle-wheel complex show Pt-Pt distances of 2.4944 (5) and 2.4892 (5) Å. The pottassium ions are seven-fold coordinated by hydrogenphosphate groups. In the crystal, O-H⋯O hydrogen bonds help to establish the packing. The Raman spectrum was recorded.

Ag(2)PdP(2)O(7).

Disilver(I) palladium(II) diphosphate, Ag(2)PdP(2)O(7), is isotypic with Na(2)PdP(2)O(7). It consists of infinite diphosphato-pallad-ate(II) [Pd(P(2)O(7))(2/2)](2-) ribbons with the Pd(II) ion in an almost square-planar coordination ( symmetry) and the P(2)O(7) group exhibiting 2 symmetry. The [Pd(P(2)O(7))(2/2)](2-) ribbons are linked by distorted [AgO(6)] octa-hedra. (31)P-MAS NMR studies on Ag(2)PdP(2)O(7) are in accordance with one independent site for phospho-rus; its isotropic chemical shift δ(iso) = 21.5 p.p.m. is similar to that of Pd(2)P(2)O(7).