Pushing thermal conductivity to its lower limit in crystals with simple structures.

Materials with low thermal conductivity usually have complex crystal structures. Herein we experimentally find that a simple crystal structure material AgTlI2 (I4/mcm) owns an extremely low thermal conductivity of 0.25 W/mK at room temperature. To understand this anomaly, we perform in-depth theoretical studies based on ab initio molecular dynamics simulations and anharmonic lattice dynamics. We find that the unique atomic arrangement and weak chemical bonding provide a permissive environment for strong oscillations of Ag atoms, leading to a considerable rattling behaviour and giant lattice anharmonicity. This feature is also verified by the experimental probability density function refinement of single-crystal diffraction. The particularly strong anharmonicity breaks down the conventional phonon gas model, giving rise to non-negligible wavelike phonon behaviours in AgTlI2 at 300 K. Intriguingly, unlike many strongly anharmonic materials where a small propagative thermal conductivity is often accompanied by a large diffusive thermal conductivity, we find an unusual coexistence of ultralow propagative and diffusive thermal conductivities in AgTlI2 based on the thermal transport unified theory. This study underscores the potential of simple crystal structures in achieving low thermal conductivity and encourages further experimental research to enrich the family of materials with ultralow thermal conductivity.

A new series of magnetic and luminescent layered hybrid materials obtained from thianthrene phosphonic acid: M(H2O)PO3-S2C12H7 (M = Cu, Zn) and M(H2O)2(PO2OH-S2C12H7)2 (M = Mn, Co).

Four new metallophosphonates with the chemical formulae M(H2O)PO3-S2C12H7 (M = Cu, Zn) and M(H2O)2(PO2OH-S2C12H7)2 (M = Mn, Co) were synthesized using a hydrothermal route from the original bent rigid thianthrene-2-ylphosphonic acid (TPA). This organic precursor crystallizes in a non-centrosymmetric space group P212121 and presents a unique bent geometry due to the presence of two sulfur atoms in its rigid platform architecture. Obtained as single crystal and polycrystalline powders, the structures of the four hybrid materials were solved using X-ray diffraction on single crystals in a monoclinic P21/c space group. These compounds adopt a lamellar structure consisting of one inorganic subnetwork alternating with a 'sawtooth' double organic -S2C12H7 subnetwork. The inorganic layers of these compounds are made of (PO3C) or partially deprotonated (PO2OHC) tetrahedra connected by the apices to isolated ZnO3(H2O) tetrahedra, Cu2O6(H2O)2 copper dimers and cobalt and manganese MO4(H2O)2 octahedra, where the latter two exhibit an isotype structure. Thermogravimetric analysis was performed to confirm the amount of water molecules present in the formula, to track the dehydration process of the structures, and to evaluate their thermal stability. The magnetic properties of the copper, cobalt, and manganese-based materials were investigated from 2 K to 300 K by using a SQUID magnetometer revealing dominant antiferromagnetic interactions with Weiss temperatures of -8.0, -10, and -1 K, respectively. These magnetic behaviors were further corroborated by first-principles simulations based on Density Functional Theory (DFT). Finally, the absorption and photoluminescence properties of both the ligand and hybrid materials were investigated, revealing diverse excitation and recombination mechanisms. The organic moiety based on thianthrene significantly influenced the absorption and emission, with additional peaks attributed to transition metals. Singlet and triplet states recombination were observed, accompanied by an unidentified quenching mechanism affecting the triplet state lifetime.

Evidence of symmetry breaking in a Gd2 di-nuclear molecular polymer.

A chiral 3D coordination compound, [Gd2(L)2(ox)2(H2O)2], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j-J coupling evident in the 5p core level spectra of Gd metal. Indications of spin-orbit coupling are consistent with the absence of inversion symmetry due to the ligand field. Density functional theory predicts antiferromagnet alignment of the Gd2 dimers and a band gap of the compound consistent with optical absorption.

Discovery of a Low Thermal Conductivity Oxide Guided by Probe Structure Prediction and Machine Learning.

We report the aperiodic titanate Ba10 Y6 Ti4 O27 with a room-temperature thermal conductivity that equals the lowest reported for an oxide. The structure is characterised by discontinuous occupancy modulation of each of the sites and can be considered as a quasicrystal. The resulting localisation of lattice vibrations suppresses phonon transport of heat. This new lead material for low-thermal-conductivity oxides is metastable and located within a quaternary phase field that has been previously explored. Its isolation thus requires a precisely defined synthetic protocol. The necessary narrowing of the search space for experimental investigation was achieved by evaluation of titanate crystal chemistry, prediction of unexplored structural motifs that would favour synthetically accessible new compositions, and assessment of their properties with machine-learning models.

Insight into the structural, elastic and electronic properties of a new orthorhombic 6O-SiC polytype.

Different polytypes of SiC are described and predicted in literature. Here, we report the first occurrence of an orthorhombic 6O-SiC polytype as rock-forming mineral in the nickel laterite mine of Tiebaghi (New Caledonia). This new class of SiC crystallizes in the space group Cmc21 with 12 atoms per unit cell [a = 3.0778(6) Å, b = 5.335(2) Å, c = 15.1219(6) Å, α = 90°, ß = 90°, γ = 120°]. The density of 6O-SiC is about 3.22 g/cm3 and the calculated indirect bandgap at room temperature of 3.56 eV is identical to 6H-SiC. Our results suggest that 6O-SiC is the intermediate state in the wurtzite to rocksalt transformation of 6H-SiC.

Cascading transitions toward unconventional charge density wave states in the quasi-two-dimensional monophosphate tungsten bronze P4W16O56.

Single crystals of the m = 8 member of the low-dimensional monophosphate tungsten bronzes (PO2)4(WO3)2m family were grown by chemical vapour transport technique and the high crystalline quality obtained allowed a reinvestigation of the physical and structural properties. Resistivity measurements revealed three anomalies at T C1 = 258 K, T C2 = 245 K and T C3 = 140 K, never observed until now. Parallel X-ray diffraction investigations showed a specific signature associated with three structural transitions, i.e. the appearance of different sets of satellite reflections below T C1, T C2 and T C3. Several harmonics of intense satellite reflections were observed, reflecting the non-sinusoidal nature of the structural modulations and a strong electron-phonon coupling in the material. These transitions could be associated with the formation of three successive unconventional charge density wave states.

M(H2O)(PO3C10H6OH)·(H2O)0.5 (M = Co, Mn, Zn, Cu): a new series of layered metallophosphonate compounds obtained from 6-hydroxy-2-naphthylphosphonic acid.

Four new metallophosphonates M(H2O)(PO3C10H6OH)·(H2O)0.5 (M = Mn, Co, Cu, Zn) were obtained as single crystal and polycrystalline powders by hydrothermal synthesis from the precursors 6-hydroxy-2-naphthylphosphonic acid and the corresponding metal salts. These analogous hybrids crystalized in the space group P121/c1 in a lamellar structure. Their layered structures consisted of inorganic [M(H2O)(PO3C)] layers stacked with organic bilayers of 6-hydroxy-2-naphthyl moieties "HO-C10H6" and free water molecules. Their structures were determined by single crystal X-ray diffraction and confirmed by powder X-ray diffraction and Le Bail refinement for the powder sample. The removal of water upon heating at 250 °C was studied by thermogravimetric analysis and temperature-dependent powder X-ray diffraction. Their magnetic properties were studied by SQUID magnetometry and show antiferromagnetic behavior for the Co analogue and the occurrence of a canted antiferromagnetic order at TN = 12.2 K for the Mn analogue. The Cu compound displayed an unprecedented ferromagnetic behavior. Their absorption and luminescence properties were investigated and revealed that the ligand and the compounds displayed a common behavior below a wavelength of 400 nm. Specific absorption bands were found in the compounds with Co2+ and Cu2+ at 539 nm and 849 nm, respectively. Moreover, particular luminescence bands were found for the compounds with Mn2+, Co2+ and Zn2+ at 598 nm, 551 nm and 530 and 611 nm, respectively.

Deciphering local complex order by HAADF in a disordered mixed polyanion iron oxide: Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25.

A layered iron compound involving two divalent polyanions (carbonate and sulfate anions) was synthesized by solid state chemistry in a closed ampule in the form of a ceramic. The Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25 compound derives from the third term of the Ruddlesden and Popper family, Sr4Fe3O10. A multiscale approach through transmission electron microscopy (TEM) and powder neutron diffraction (PND) studies shows that SO4 and CO3 groups substitute for the iron polyhedron of the central layer of the perovskite blocks and the absence of long range ordering between sulfate and carbonates and FeO5 groups. Nevertheless, waves disturbing the expected periodicity of the atomic layer are evidenced in HAADF images. An accurate analysis of these images provides a view of the local cationic order correlated with SO4 and CO3 for FeO5 substitution.

Combining Multiscale Approaches for the Structure Determination of an Iron Layered Oxysulfate: Sr4Fe2.5O7.25(SO4)0.5.

The new iron layered oxysulfate Sr4Fe2.5O7.25(SO4)0.5 has been prepared by a solid-state reaction in closed ampules into the form of ceramics and single crystals. Its atomic structure has been solved by means of spectroscopy, diffraction techniques, and high-resolution electron microscopy. Sr4Fe2.5O7.25(SO4)0.5 is a layered structure that derives from the Ruddelsden-Popper (RP) phases with the layer stacking sequence SrO/SrFeO2.5/SrFe0.5(SO4)0.5O1.25/SrFeO2.5. Within the mixed Fe3+/SO42- layer, the sulfur atoms are slightly shifted from the B site of the perovskite and each sulfate group shares two corners with iron pyramids in the basal plan without any order phenomenon. The electronic conductivity is thermally activated, while no ionic conductivity is detected.

Novel Layered Supercell Structure from Bi2AlMnO6 for Multifunctionalities.

Layered materials, e.g., graphene and transition metal (di)chalcogenides, holding great promises in nanoscale device applications have been extensively studied in fundamental chemistry, solid state physics and materials research areas. In parallel, layered oxides (e.g., Aurivillius and Ruddlesden-Popper phases) present an attractive class of materials both because of their rich physics behind and potential device applications. In this work, we report a novel layered oxide material with self-assembled layered supercell structure consisting of two mismatch-layered sublattices of [Bi3O3+δ] and [MO2]1.84 (M = Al/Mn, simply named BAMO), i.e., alternative layered stacking of two mutually incommensurate sublattices made of a three-layer-thick Bi-O slab and a one-layer-thick Al/Mn-O octahedra slab in the out-of-plane direction. Strong room-temperature ferromagnetic and piezoelectric responses as well as anisotropic optical property have been demonstrated with great potentials in various device applications. The realization of the novel BAMO layered supercell structure in this work has paved an avenue toward exploring and designing new materials with multifunctionalities.

Crystal structures of η''-Cu3+xSi and η'''-Cu3+xSi.

The binary phase diagram of Cu-Si is unexpectedly complex in the vicinity of Cu3+xSi. The low-temperature region contains three closely related incommensurately modulated phases denoted, in order of increasing temperature of stability, η''', η'' and η'. The structure analysis of η' has been reported previously [Palatinus et al. (2011). Inorg. Chem. 50, 3743]. Here the structure model for the phases η'' and η''' is reported. The structures could be solved in superspace, but no superspace structure model could be constructed due to the complexity of the modulation functions. Therefore, the structures were described in a supercell approximation, which involved a 4 × 4 × 3 supercell for the η'' phase and a 14 × 14 × 3 supercell for the η''' phase. Both structures are very similar and differ only by a subtle symmetry lowering from η'' to η'''. A comparison of the structure models of η'' and η''' with the reported structure of η' suggests that the reported structure model of η' contains an incorrect assignment of atomic types.

Linear, Hypervalent Se34- Units and Unprecedented Cu4Se9 Building Blocks in the Copper(I) Selenide Ba4Cu8Se13.

Single-crystal and polycrystalline Ba4Cu8Se13 were synthesized; the average crystal structure was solved by single-crystal X-ray diffraction, and the structural model was confirmed by a detailed electron microscopy study of polycrystalline Ba4Cu8Se13. The title compound can be rationalized as (Ba2+)4(Cu+)8(Se2-)2(Se22-)4(Se34-) and crystallizes in a new structure type (space group C2/c with a = 9.171(8) Å, b = 9.146(8) Å, c = 27.35(3) Å, ß = 93.21(3)°, and V = 2291 Å3). It contains unprecedented Cu4Se9 fragments with planar Cu rectangles. These fragments form two-dimensional layers via regular (2c-2e) Se-Se bonds. Two of these layers are then connected in the third dimension via linear, hypervalent Se34- units, resulting in "sandwichlike", layered building blocks, which are stacked along c and separated by Ba. Ba4Cu8Se13 is the first example where Se22- and Se34- groups coexist. We were able to visualize the crystal structure by recording HAADF images, which clearly reveal the Cu4Se9 fragments and linear Se34- units. The title compound is a charge-balanced semiconductor and possesses a large Seebeck coefficient (380 µV K-1 at 200 K) and a low thermal conductivity (0.77 W m-1 K-1 at 200 K)-two requirements for efficient thermoelectric materials.

Crystal structure of µ-cyanido-1:2κ(2) N:C-dicyanido-1κC,2κC-bis-(quinolin-8-amine-1κ(2) N,N')-2-silver(I)-1-silver(II): rare occurrence of a mixed-valence Ag(I,II) compound.

The title dinuclear complex, [Ag2(CN)3(C9H8N2)2], may be considered as an Ag(II) compound with the corresponding metal site coordinated by two bidentate quinolin-8-amine mol-ecules, one cyanide group and one dicyanidoargentate(I) anion, [Ag(CN)2](-). Since this latter ligand contains an Ag(I) atom, the complex should be a class 1 or class 2 mixed-valence compound, according to the Robin-Day classification. The Ag(II) atom is six-coordinated in a highly distorted octa-hedral geometry, while the Ag(I) atom displays the expected linear geometry. In the crystal, the amino groups of the quinolin-8-amine ligands form N-H⋯N hydrogen bonds with the N atoms of the non-bridging cyanide ligands, forming a two-dimensional network parallel to (102). The terminal cyanide ligands are not engaged in polymeric bonds and the title compound is an authentic mol-ecular complex. The title mol-ecule is thus a rare example of a stable Ag(I,II) complex, and the first mixed-valence Ag(I,II) mol-ecular complex characterized by X-ray diffraction.

Magnetodielectric Effect in Crystals of the Noncentrosymmetric CaOFeS at Low Temperature.

Single crystals of the stoichiometric iron calcium oxysulfide CaOFeS have been grown by a solid-state reaction. Structural analysis of CaOFeS at room temperature by combining single-crystal X-ray diffraction data and transmission electron microscopy leads to a stoichiometric hexagonal noncentrosymmetric P63mc layered structure isostructural to CaOZnS. It is built from alternating layers made of FeOS3 tetrahedra sharing sulfur apexes and stacked with Ca(2+) planes. All Fe-O bonds are parallel to the stacking axis; this breaks the centrosymmetry, leading to a polar structure. The dielectric measurements reveal the existence of a magnetodielectric effect near 33 K in good agreement with the Neel temperature, as evidenced near 35 K by specific heat measurements reported by a different group.

Silver-based hybrid materials from meta- or para-phosphonobenzoic acid: influence of the topology on silver release in water.

Three novel silver-based metal-organic frameworks materials, which were synthesized from either 3-phosphono or 4-phosphonobenzoic acid and silver nitrate, are reported. The novel hybrids were synthesized under hydrothermal conditions; the pH of the reaction media was controlled by adding different quantities of urea thereby producing different topologies. Compound 1 (Ag3(4-PO3-C6H4-COO)), synthesized in the presence of urea, exhibits a compact 3D structure in which both phosphonic acid and carboxylic acid functional groups are linked to the silver-based inorganic network. Compound 2 (Ag(4-PO3H-C6H4-COOH)), which was synthesized at lower pH (without urea), has a layered structure in which only the phosphonic acid functional groups from 4-phosphonobenzoic acid moieties are linked to the silver inorganic network; the carboxylic acid groups being engaged in hydrogen bonds. Finally, material 3 (Ag(3-PO3H-C6H4-COOH)) was synthesized from 3-phosphonobenzoic acid and silver nitrate without urea. This material 3 features a layered structure exhibiting carboxylic acid functional groups linked via hydrogen bonds in the interlayer space. After the full characterization of these materials (single X-ray structure, IR, TGA), their ability to release silver salts in aqueous environment was measured. Silver release, determined in aqueous solution by cathodic stripping voltammetry, shows that the silver release capacity of these materials is dependent on the topology of the hybrids. The more compact structure 1 is extremely stable in water with only trace levels of silver ions being detected. On the other hand, compounds 2 and 3, in which only the phosphonic acid functional groups were bonded to the inorganic network, released larger quantities of silver ions into aqueous solution. These results which were compared with the silver release of the previously described compound 4 (Ag6(3-PO3-C6H4-COO)2). The results clearly show that the release capacity of silver-based metal organic framework can be tuned by modifying their topology which, in the present study, is governed by the regio-isomer of the organic precursor and the synthetic conditions under which the hybrids are prepared.

Metamaterial filters at optical-infrared frequencies.

We propose two distinctive designs of metamaterials demonstrating filtering functions in the visible and near infrared region. Since the emissivity is related to the absorption of a material, these filters would then offer a high emissivity in the visible and near infrared, and a low one beyond those wavelengths. Usually, such a system find their applications in the thermo-photovoltaics field as it can find as well a particular interest in optoelectronics, especially for optical detection. Numerical analysis has been performed on common metamaterial designs: a perforated metallic plate and a metallic cross grating. Through all these structures, we have demonstrated the various physical phenomena contributing to a reduction in the reflectivity in the optical and near infrared region. By showing realistic geometric parameters, the structures were not only designed to demonstrate an optical filtering function but were also meant to be feasible on large surfaces by lithographic methods such as micro contact printing or nano-imprint lithography.

Monophosphate tungsten bronzes with pentagonal tunnels: reinvestigation through the peephole of the superspace.

The large family of monophosphate tungsten bronzes with pentagonal tunnels (MPTBp), (PO2)4(WO3)2m with m ranging from 4 to 14, can be considered as modular structures via a description with (PO2)2(WO3)m modules related together by a symmetry operation and alternating along the z axis. Following the success of the application of the superspace for the description of the lillianites homologous series, a (3+1)-dimensional superspace model is efficiently defined to unify the structural analysis of the MPTBp. The (3+1)-dimensional model reveals hidden common characteristics such as the symmetry. An evaluation of the model for six well known members of the series was carried out from experimental data collected to this aim.

Structural study of hydrated/dehydrated manganese thiophene-2,5-diphosphonate metal organic frameworks, Mn2(O3P-C4H2S-PO3)·2H2O.

Synthesis of thiophene-2,5-diphosphonic acid 2 is reported, and its use for synthesis of the original pristine materials Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 3 is reported. The structure of material 3 has been fully resolved from single-crystal X-ray diffraction. Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 3 crystallizes in a monoclinic cell (space group P2) with the following parameters: a = 11.60(1) Å, b = 4.943(5) Å, c = 19.614(13) Å, ß = 107.22°. A noticeable feature of the structure of compound 3 is the orientation of the thiophene heterocycles that adopt two different orientations in two successive layers (along c). Thermal analysis of compound 3 indicates that the water molecules are easily removed from 160 to 230 °C while the dehydrated structure is stable up to 500 °C. The dehydrated compound obtained from 3 can be rehydrated to give the polymorphic compound Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 4, which crystallizes in an orthorhombic cell (space group Pnam) with the following parameters: a = 7.5359(3) Å, b = 7.5524(3) Å, c = 18.3050(9) Å. The main difference between the structures of 3 and 4 arises from both the orientation of the thiophene rings (herringbone-type organization in 4) and the structure of the inorganic layers. The thiophene-2,5-diphosphonic acid moieties engaged in materials 3 and 4 adopt a different orientation likely due to rotation around the P-C bonds and via the dehydrated state 5, which is likely more flexible than the hydrated states. Study of the magnetic properties performed on compound 3 and 4 and on the dehydrated compounds Mn(2)(O(3)P-C(4)H(2)S-PO(3)) 5 complemented by the structural study has permitted us to characterize the antiferromagnetic ground state of sample 3, a weak ferromagnetic component in sample 4, and complete paramagnetic behavior in sample 5.

Unified (3 + 1)-dimensional superspace description of the 2212-type stair-like [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] family of compounds.

The (3 + 1)-dimensional superspace approach is applied to describe and refine a series of sheared compounds related to layered high T(c) superconducting oxides. Two commensurate members (m = 4, 5) of the 2212 stair-like [Bi(2)Sr(3)Fe(2)O(9)](m)[Bi(4)Sr(6)Fe(2)O(16)] family of compounds, previously studied using single-crystal diffraction data, are analyzed. A common average unit cell has been identified and a composition-dependent modulation wavevector is proposed. The model is built using only three independent atomic domains, one for the metal atoms and two for the O atoms. The three Sr, Bi and Fe species are described using close-connected crenel-like functions forming a continuous atomic domain along the internal space. The two oxygen domains are represented by crenel functions and the displacive modulation functions are built up by Legendre polynomials recently implemented in the program JANA2006. Surprisingly, the results of the refinements show a striking similarity of the displacive modulations for the two compounds analyzed, indicating that a unique model can be used to describe the correlations between the atomic displacements of the 2212 stair-like series. This final model is then applied to predict the structure of new members of the family.

(Z,1S,10aR)-(-)-Menthyl 1-hy-droxy-1,2,3,5,6,7,10,10a-octa-hydro-pyrrolo-[1,2-a]azocine-10a-carboxyl-ate.

The structure determination confirms the stereochemistry of the title compound, C(21)H(35)NO(3), obtained as an inter-mediate in the enanti-oselective synthesis of de-oxy-nojirimicine analogs. The system contains a pyrrolo-[1,2-a]azocine backbone, which was synthesized by a domino process involving a [2,3]-sigmatropic rearrangement. The incorporation of a chiral auxiliary (-)-menthyl, whose stereocentres are not involved during the synthesis, enables the assignation of absolute configuration. The crystal structure features O-H⋯O hydrogen bonds involving the hy-droxy groups as donors and the carbonyl groups as acceptors, which link the mol-ecules into chains running along [010].