Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine.

A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq23-)(H5O2+), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

Ba3CrN3H: A New Nitride-Hydride with Trigonal Planar Cr4.

The nitride-hydride Ba3CrN3H was obtained in single crystalline form using flux growth techniques based on alkaline earth metals. Ba3CrN3H crystallizes in the hexagonal space group P63/ m (Nr 176), with the lattice parameters a = 8.0270(2) Å, c = 5.6240(1) Å, and Z = 2. The structure comprises [CrN3]5- trigonal planar units and [HBa6]11+ octahedral units. The presence of anionic hydrogen in the structure has been verified by 1H NMR experiments. DFT calculations show that the addition of hydrogen increases the stability of the phase versus Ba3CrN3. The two d-electrons of Cr4+ are located in the nonbonding d z2 orbital, rendering Ba3CrN3H nonmagnetic and insulating.

Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2.

Single crystals of a new family of layered lanthanide oxychlorides, Ba3Ln2O5Cl2 (Ln = Gd-Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)-4.4541(1) Å and c = 24.5108(7)-24.8448(9) Å. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. The synthesis of this family suggests a route to other potential multianion phases.

Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation.

Hybrid organic-inorganic metal halide perovskites possess exceptional structural tunability, with three- (3D), two- (2D), one- (1D), and zero-dimensional (0D) structures on the molecular level all possible. While remarkable progress has been realized in perovskite research in recent years, the focus has been mainly on 3D and 2D structures, with 1D and 0D structures significantly underexplored. The synthesis and characterization of a series of low-dimensional organic tin bromide perovskites with 1D and 0D structures is reported. Using the same organic and inorganic components, but at different ratios and reaction conditions, both 1D (C4 N2 H14 )SnBr4 and 0D (C4 N2 H14 Br)4 SnBr6 can be prepared in high yields. Moreover, photoinduced structural transformation from 1D to 0D was investigated experimentally and theoretically in which photodissociation of 1D metal halide chains followed by structural reorganization leads to the formation of a more thermodynamically stable 0D structure.

Assembling hierarchical cluster solids with atomic precision.

Hierarchical solids created from the binary assembly of cobalt chalcogenide and iron oxide molecular clusters are reported. Six different molecular clusters based on the octahedral Co6E8 (E = Se or Te) and the expanded cubane Fe8O4 units are used as superatomic building blocks to construct these crystals. The formation of the solid is driven by the transfer of charge between complementary electron-donating and electron-accepting clusters in solution that crystallize as binary ionic compounds. The hierarchical structures are investigated by single-crystal X-ray diffraction, providing atomic and superatomic resolution. We report two different superstructures: a superatomic relative of the CsCl lattice type and an unusual packing arrangement based on the double-hexagonal close-packed lattice. Within these superstructures, we demonstrate various compositions and orientations of the clusters.

Ferromagnetic ordering in superatomic solids.

In order to realize significant benefits from the assembly of solid-state materials from molecular cluster superatomic building blocks, several criteria must be met. Reproducible syntheses must reliably produce macroscopic amounts of pure material; the cluster-assembled solids must show properties that are more than simply averages of those of the constituent subunits; and rational changes to the chemical structures of the subunits must result in predictable changes in the collective properties of the solid. In this report we show that we can meet these requirements. Using a combination of magnetometry and muon spin relaxation measurements, we demonstrate that crystallographically defined superatomic solids assembled from molecular nickel telluride clusters and fullerenes undergo a ferromagnetic phase transition at low temperatures. Moreover, we show that when we modify the constituent superatoms, the cooperative magnetic properties change in predictable ways.

Structural trends and itinerant magnetism of the new cage-structured compound HfMn2Zn20.

A new cage-structured compound-HfMn2Zn20-belonging to theAB2C20(A, B= transition or rare earth metals, andC= Al, Zn, or Cd) family of structures has been synthesized via the self-flux method. The new compound crystallizes in the space groupFd3¯mwith lattice parametera≈ 14.0543(2) Å (Z= 8) and exhibits non-stoichiometry due to Mn/Zn mixing on the Mn-site and an underoccupied Hf-site. The structure refines to Hf0.93Mn1.63Zn20.37and follows lattice size trends when compared to other HfM2Zn20(M= Fe, Co, and Ni) structures. The magnetic measurements show that this compound displays a modified Curie-Weiss behavior with a transition temperature around 22 K. The magnetization shows no saturation, a small magnetic moment, and near negligible hysteresis, all signs of itinerant magnetism. The Rhodes-Wohlfarth ratio and the spin fluctuation parameters ratio both confirm the itinerant nature of the magnetism in HfMn2Zn20.

Single crystal elasticity of natural topaz at high-temperatures.

Topaz is an aluminosilicate mineral phase stable in the hydrothermally altered pegmatitic rocks and also in subducted sedimentary lithologies. In nature, topaz often exhibits solid solution between fluorine and hydrous end members. We investigated elasticity of naturally occurring single crystal topaz (Al2SiO4F1.42(OH)0.58) using Resonant Ultrasound Spectroscopy. We also explored the temperature dependence of the full elastic constant tensor. We find that among the various minerals stable in the Al2O3-SiO2-H2O ternary system, topaz exhibits moderate elastic anisotropy. As a function of temperature, the sound velocity of topaz decreases with [Formula: see text] and [Formula: see text] being -3.10 and -2.30 × 10-4 km/s/K. The elasticity and sound velocity of topaz also vary as a function of OH and F content. The effect of composition ([Formula: see text]) on the velocity is equally important as that of the effect of temperature. We also note that the Debye temperature ([Formula: see text]) of topaz at room temperature condition is 910 K and decreases at higher temperature. The Debye temperature shows positive correlation with density of the mineral phases in the Al2O3-SiO2-H2O ternary system.

Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency.

Single crystalline zero-dimensional (0D) organic-inorganic hybrid materials with perfect host-guest structures have been developed as a new generation of highly efficient light emitters. Here we report a series of lead-free organic metal halide hybrids with a 0D structure, (C4N2H14X)4SnX6 (X = Br, I) and (C9NH20)2SbX5 (X = Cl), in which the individual metal halide octahedra (SnX64-) and quadrangular pyramids (SbX52-) are completely isolated from each other and surrounded by the organic ligands C4N2H14X+ and C9NH20+, respectively. The isolation of the photoactive metal halide species by the wide band gap organic ligands leads to no interaction or electronic band formation between the metal halide species, allowing the bulk materials to exhibit the intrinsic properties of the individual metal halide species. These 0D organic metal halide hybrids can also be considered as perfect host-guest systems, with the metal halide species periodically doped in the wide band gap matrix. Highly luminescent, strongly Stokes shifted broadband emissions with photoluminescence quantum efficiencies (PLQEs) of close to unity were realized, as a result of excited state structural reorganization of the individual metal halide species. Our discovery of highly luminescent single crystalline 0D organic-inorganic hybrid materials as perfect host-guest systems opens up a new paradigm in functional materials design.

Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C4N2H14Br)4SnBrxI6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBrxI6-x4-, x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C4N2H14Br-. The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl10O17:Eu2+) can exhibit high color rendering indexes of up to 85.

Bulk assembly of organic metal halide nanotubes.

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C6H13N4)3Pb2Br7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb2Br95-) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C6H13N4+). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ∼7%. Having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.

Interacting nanoscale magnetic superatom cluster arrays in molybdenum oxide bronzes.

In this study, we examine several reduced ternary molybdates in the family of yellow rare earth molybdenum bronzes produced by electrochemical synthesis with composition LnMo16O44. These compounds contain an array of electrically isolated but magnetically interacting multi-atom clusters with composition Mo8O36. These arrayed superatom clusters support a single hole shared among the eight molybdenum atoms in the unit, corresponding to a net spin moment of 1µB, and exhibit magnetic exchange between the units via the MoO4 tetrahedra (containing Mo6+ ions) and the LnO8 cubes (containing Ln3+ ions). The findings presented here expand on the physics of the unusual collective properties of multi-atom clusters and extend the discussion of such assemblages to the rich structural chemistry of molybdenum bronzes.

Electrochemical Doping of Halide Perovskites with Ion Intercalation.

Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

Influence of grain boundary characteristics on thermal stability in nanotwinned copper.

High density grain boundaries provide high strength, but may introduce undesirable features, such as high Fermi levels and instability. We investigated the kinetics of recovery and recrystallization of Cu that was manufactured to include both nanotwins (NT) and high-angle columnar boundaries. We used the isothermal Johnson-Mehl-Avrami-Kolmogorov (JMAK) model to estimate activation energy values for recovery and recrystallization and compared those to values derived using the non-isothermal Kissinger equation. The JMAK model hinges on an exponent that expresses the growth mechanism of a material. The exponent for this Cu was close to 0.5, indicating low-dimensional microstructure evolution, which is associated with anisotropic twin coarsening, heterogeneous recrystallization, and high stability. Since this Cu was of high purity, there was a negligible impurity-drag-effect on boundaries. The twin coarsening and heterogeneous recrystallization resulted from migration of high-angle columnar boundaries with their triple junctions in one direction, assisted by the presence of high concentration vacancies at boundaries. Analyses performed by electron energy loss spectroscopy of atomic columns at twin boundaries (TBs) and in the interior showed similar plasma peak shapes and L3 edge positions. This implies that values for conductivity and Fermi level are equal for atoms at TBs and in the interior.

High hardness in the biocompatible intermetallic compound ß-Ti3Au.

The search for new hard materials is often challenging, but strongly motivated by the vast application potential such materials hold. Ti3Au exhibits high hardness values (about four times those of pure Ti and most steel alloys), reduced coefficient of friction and wear rates, and biocompatibility, all of which are optimal traits for orthopedic, dental, and prosthetic applications. In addition, the ability of this compound to adhere to ceramic parts can reduce both the weight and the cost of medical components. The fourfold increase in the hardness of Ti3Au compared to other Ti-Au alloys and compounds can be attributed to the elevated valence electron density, the reduced bond length, and the pseudogap formation. Understanding the origin of hardness in this intermetallic compound provides an avenue toward designing superior biocompatible, hard materials.

Fully Printed Halide Perovskite Light-Emitting Diodes with Silver Nanowire Electrodes.

Printed organometal halide perovskite light-emitting diodes (LEDs) are reported that have indium tin oxide (ITO) or carbon nanotubes (CNTs) as the transparent anode, a printed composite film consisting of methylammonium lead tribromide (Br-Pero) and poly(ethylene oxide) (PEO) as the emissive layer, and printed silver nanowires as the cathode. The fabrication can be carried out in ambient air without humidity control. The devices on ITO/glass have a low turn-on voltage of 2.6 V, a maximum luminance intensity of 21014 cd m(-2), and a maximum external quantum efficiency (EQE) of 1.1%, surpassing previous reported perovskite LEDs. The devices on CNTs/polymer were able to be strained to 5 mm radius of curvature without affecting device properties.

Nanoscale atoms in solid-state chemistry.

We describe a solid-state material formed from binary assembly of atomically precise molecular clusters. [Co6Se8(PEt3)6][C60]2 and [Cr6Te8(PEt3)6][C60]2 assembled into a superatomic relative of the cadmium iodide (CdI2) structure type. These solid-state materials showed activated electronic transport with activation energies of 100 to 150 millielectron volts. The more reducing cluster Ni9Te6(PEt3)8 transferred more charge to the fullerene and formed a rock-salt-related structure. In this material, the constituent clusters are able to interact electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.