La26Ge19M5O5 (M = Ag, Cu): Rare-Earth Metal Suboxide Superconductors with [La18O5] Cluster Units.

Herein we report two reduced rare-earth metal-based superconductors, La26Ge19M5O5 (M = Ag, Cu), that feature an unprecedented [La18O5] cluster composed of five oxygen-centered [La6O] octahedra condensed through shared faces and capped with [Ge4] butterfly rings. The structure, determined by single-crystal X-ray diffraction, crystallizes in a tetragonal space group (P4/nmm), with a = 15.508(2) Å and c = 11.238(2) Å. Resistivity and magnetic susceptibility measurements show onsets of superconductivity at Tc = 5.4 and 6.4 K for the Ag and Cu compounds, respectively. Applying high pressures, up to 1.3 GPa, results in increased superconducting transition temperatures (Tc = 6.8 K for Ag and 7.2 K for Cu compounds), with no sign of saturation.

Optical properties and lattice dynamics of a novel allotrope of orthorhombic elemental germanium.

Optical and vibrational properties of a novel allotrope of elemental germanium Ge(oP32), which crystallizes in the structure corresponding to the orthorhombic space group Pbcm, are studied experimentally by means of absorption and polarized Raman scattering measurements and theoretically using the first principles density functional theory. Material is found to be a direct band gap semiconductor with E g = 0.33 eV. Out of theoretically predicted 48 Raman-active modes, 27 are observed in the spectra and assigned to the specific lattice eigenmodes of the crystal based on their symmetry and a comparison with the results of first principles lattice dynamics calculations. Remarkably, the highest frequency vibration is observed at 316 cm-1, that is higher than the cubic crystalline [Formula: see text]-Ge mode at 300 cm-1. Exceptional sharpness of observed phonon lines (between 0.8 and 2.5 cm-1 at T = 10 K) implies excellent crystallinity of Ge(oP32) crystals.

Narrow Gap Semiconducting Germanium Allotrope from the Oxidation of a Layered Zintl Phase in Ionic Liquids.

A metastable germanium allotrope, Ge(oP32), was synthesized as polycrystalline powders and single crystals from the mild-oxidation/delithiation of Li7Ge12 in ionic liquids. Its crystal structure, from single crystal X-ray diffraction ( Pbcm, a = 8.1527(4) Å, b = 11.7572(5) Å, c = 7.7617(4) Å), features a complex covalent network of 4-bonded Ge, resulting from a well-ordered topotactic oxidative condensation of [Ge12]7- layers. It is a diamagnetic semiconductor ( Eg = 0.33 eV), and transforms exothermically and irreversibly to α-Ge at 363 °C. This demonstrates the potential of ionic liquids as reactive media in the mild oxidation of Zintl phases to new highly crystallized modifications of elements and simple compounds.

Lattice Dynamics of the Rhombohedral Polymorphs of CaSi2.

The structures of two trigonal-rhombohedral CaSi2 polymorphs (space group R3̅m) were studied by X-ray diffraction and polarized Raman scattering spectroscopy. Raman-active even-parity vibrational modes of A1g and Eg are unambiguously identified and assigned to the specific lattice eigenmodes. Experimental data are found to be in very good agreement with those predicted by density functional theory lattice dynamics calculations. The transformation of 6R structural modification of CaSi2 into its 3R polymorph, by high-temperature annealing in vacuum is also reported.

Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells.

We report an effective solvent engineering process to enable controlled perovskite crystal growth and a wider window for processing uniform and dense methyl ammonium lead iodide (MAPbI3) perovskite films. Planar heterojunction solar cells fabricated with this method demonstrate hysteresis-free performance with a power conversion efficiency around 10%. The crystal structure of an organic-based Pb iodide intermediate phase is identified for the first time, which is critical in controlling the crystal growth and optimizing thin film morphology.

Nb2O2F3: a reduced niobium (III/IV) oxyfluoride with a complex structural, magnetic, and electronic phase transition.

A new niobium oxyfluoride, Nb2O2F3, synthesized through the reaction of Nb, SnO, and SnF2 in Sn flux, within welded Nb containers, crystallizes in a monoclinic structure (space group: I2/a; a = 5.7048(1)Å, b = 5.1610(1)Å, c = 12.2285(2)Å, ß = 95.751(1)°). It features [Nb2X10] units (X = O, F), with short (2.5739(1) Å) Nb-Nb bonds, that are linked through shared O/F vertices to form a 3D structure configurationally isotypic to ζ-Nb2O5. Nb2O2F3 undergoes a structural transition at ∼90 K to a triclinic structure (space group: P1̅; a = 5.1791(5)Å, b = 5.7043(6)Å, c = 6.8911(7)Å, α = 108.669(3)°, ß = 109.922(2)°, γ = 90.332(3)°). The transition is described as a disproportionation or charge ordering of [Nb2](7+) dimers: (2[Nb2](7+) → [Nb2](6+) + [Nb2](8+)), resulting in doubly (2.5000(9) Å) and singly bonded (2.6560(9) Å) Nb2 dimers. The structural transition is accompanied by an unusual field-independent "spin-gap-like" magnetic transition.

Synthesis, structure, and superconductivity in the new-structure-type compound: SrPt6P2.

A metal-rich ternary phosphide, SrPt(6)P(2), with a unique structure type was synthesized at high temperatures. Its crystal structure was determined by single-crystal X-ray diffraction [cubic space group Pa3̅; Z = 4; a = 8.474(2) Å, and V = 608.51(2) Å(3)]. The structure features a unique three-dimensional anionic (Pt(6)P(2))(2-) network of vertex-shared Pt(6)P trigonal prisms. The Sr atoms occupy a 12-coordinate (Pt) cage site and form a cubic close-packed (face-centered-cubic) arrangement, and the P atoms formally occupy tetrahedral interstices. The metallic compound becomes superconducting at 0.6 K, as evidenced by magnetic and resistivity measurements.

Ba(1-x)Na(x)Ti2Sb2O (0.0 ≤ x ≤ 0.33): a layered titanium-based pnictide oxide superconductor.

A new layered Ti-based pnictide oxide superconductor, Ba(1-x)Na(x)Ti(2)Sb(2)O (0.0 ≤ x ≤ 0.33), is reported. X-ray studies revealed that it crystallizes in the tetragonal CeCr(2)Si(2)C structure. The undoped parent compound, BaTi(2)Sb(2)O [P4/mmm; a = 4.1196(1) Å; c = 8.0951(2) Å], exhibits a charge density wave (CDW)/spin density wave (SDW) transition at 54 K. Upon chemical doping with Na, the CDW/SDW transition is systematically suppressed, and superconductivity arises with the critical temperature (T(c)) increasing to 5.5 K. Bulk superconductivity was confirmed by resistivity, magnetic, and heat capacity measurements. Like the high-T(c) cuprates and the iron pnictides, the superconductivity in BaTi(2)Sb(2)O arises from an ordered state. Similarities and differences between BaTi(2)Sb(2)O and the cuprate and iron pnictide superconductors are discussed.

Synthesis and electron holography studies of single crystalline nanostructures of clathrate-II phases K(x)Ge136 and Na(x)Si136.

Crystalline nanosized particles of clathrate-II phases K(x)Ge(136) and Na(x)Si(136) were obtained from a dispersion of alkali metal tetrelides in ionic liquids based on DTAC/AlCl(3), which were slowly heated to 120-180 °C. The nanoparticles are bullet-shaped with typical dimensions of about 40 nm in width and 140-200 nm in length. Detailed structure investigations using high-resolution transmission electron microscopy (HRTEM) and electron holography reveal the crystallinity and dense morphology of the clathrate nanorods.

Superconducting Fe-based compounds (A1-xSrx)Fe2As2 with A=K and Cs with transition temperatures up to 37 K.

New high-T{c} Fe-based superconducting compounds, AFe2As2 with A=K, Cs, K/Sr, and Cs/Sr, were synthesized. The T{c} of KFe2As2 and CsFe2As2 is 3.8 and 2.6 K, respectively, which rises with partial substitution of Sr for K and Cs and peaks at 37 K for 50%-60% Sr substitution, and the compounds enter a spin-density-wave state with increasing electron number (Sr content). The compounds represent p-type analogs of the n-doped rare-earth oxypnictide superconductors. Their electronic and structural behavior demonstrate the crucial role of the (Fe2As2) layers in the superconductivity of the Fe-based layered systems, and the special feature of having elemental A layers provides new avenues to superconductivity at higher T{c}.

Remarkable rare-earth metal silicide oxides with planar Si6 rings.

New rare-earth silicide oxides, La10Si8O3 (1) and Ce10Si8O3 (2), were synthesized through high-temperature reactions of the pure elements under controlled oxygen atmosphere conditions. The remarkable silicides crystallize in a unique crystal structure (space group P6/mmm; a = 10.975(3) A (La) and 10.844(1) A (Ce); c = 4.680(1) A (La) and 4.561(1) A (Ce)) that features a 3-D framework of corner-shared O-centered (La/Ce)6 octahedra, reminiscent of hexagonal tungsten bronzes, with planar Si6 rings enclosed within its hexagonal channels. Band structure calculations indicate the compounds are metallic, with optimized La-Si bonds, and a benzene-like [Si6]6- anion. Compound 1 exhibits temperature independent paramagnetism. Compound 2 exhibits Curie-Weiss paramagnetism, and an antiferromagnetic ordering below 7 K.

A guest-free germanium clathrate.

The challenges associated with synthesizing expanded semiconductor frameworks with cage-like crystal structures continue to be of interest. Filled low-density germanium and silicon framework structures have distinct properties that address important issues in thermoelectric phonon glass-electron crystals, superconductivity and the possibility of Kondo insulators. Interest in empty framework structures of silicon and germanium is motivated by their predicted wide optical bandgaps of the same magnitude as quantum dots and porous silicon, making them and their alloys promising materials for silicon-based optoelectronic devices. Although almost-empty Na(1-x)Si136 has already been reported, the synthesis of guest-free germanium clathrate has so far been unsuccessful. Here we report the high-yield synthesis and characteristics of germanium with the empty clathrate-II structure through the oxidation of Zintl anions in ionic liquids under ambient conditions. The approach demonstrates the potential of ionic liquids as media for the reactions of polar intermetallic phases.

[H3N(CH2)7NH3]8(CH3NH3)2Sn(IV)Sn(II)12I46- a mixed-valent hybrid compound with a uniquely templated defect-perovskite structure.

The incorporation of H(3)N(CH(2))(7)NH(3) with CH(3)NH(3)SnI(3) resulted in the formation of a mixed-valent and semiconducting (Eg = 0.84 eV) organic-based perovskite, [H(3)N(CH(2))(7)NH(3)](8)(CH(3)NH(3))(2)Sn(iv)Sn(ii)(12)I(46), with a unique 3D defect-perovskite structure with ordered vacancies at the Sn and I sites.

Layered organic-based metal iodide-polyiodide with unique mixed-valent gold(I/III) iodide chains.

We report the synthesis, optical spectrum, and crystal and electronic structures of a new organic-inorganic hybrid compound, [(p-NH3C6H4)2CH2]4 [(AuI2)(AuI4)(I2)2(I5)2Cl4], with unique mixed-valent gold(I/III) chains. The chains feature face-shared octahedral [AuIAu(III)I6]2- units and are embedded within polyiodide layers. The new mixed-valent gold iodide crystallizes in the orthorhombic space group Pnnm, with a = 27.0703(2), b = 8.9363(5), c = 18.4280(1) angstroms, Z = 2, and exhibits an optical band gap of 0.53 eV.

Li17Ag3Sn6: a polar intermetallic pi-system with carbonate-like [AgSn3]11- anions and trefoil aromatic [Ag2Sn3]6- layers.

A new lithium silver stannide, Li17Ag3Sn6, was synthesized from high-temperature reactions of the pure elements in tantalum containers. Its crystal structure, in the space group, P31m, with a = 8.063(3) A, c = 8.509(4) A, Z = 1, features two distinct AgSn-based anionic layers. Defect graphitic layers of Ag2Sn3, with ordered vacancies at one-third of the Ag sites, are alternately stacked with Kagome-like nets of isolated trigonal planar AgSn3 units. Double layers of Li ions are sandwiched between the stacked AgSn-based layers. Theoretical calculations show unusual pi-interactions within both anionic layers, with the trigonal planar [AgSn3]11- units being isoelectronic with CO(3)2-. In addition, the chemical bonding of the layered [Ag2Sn3]6- pi-network features incompletely filled lone-pair Sn states involved in in-plane trefoil aromatic interactions. Transport and magnetic susceptibility measurements on Li17Ag3Sn6 indicate excellent metallic behavior and temperature-independent paramagnetism consistent with results from band structure calculations. The "trefoil" aromaticity, previously postulated for aromatic molecular systems, is finally observed, albeit in a polar intermetallic solid-state structure that lies at the border between metals and nonmetals.

The role of sequestering agents in the formation and structure of germanium anion cluster polymers.

Large blue-green, transparent crystalline needles of [K-(2,2)diaza-[18]-crown-6]KGe(9).3en are prepared, in high yield, from the reaction of (2,2)diaza[18]-crown-6 in toluene with a solution of "KGe(4)" in ethylenediamine (en). The compound crystallizes in the orthorhombic space group Pnma (a = 10.9763(12) A, b = 27.265(3) A, c = 13.880(1) A; Z = 4). The crystal structure of [K-(2,2)diaza-[18]-crown-6]KGe(9).2en features one-dimensional [KGe(9)](-) bare intermetallic chains formed from the linking, via exo-bonds, of nido-Ge(9)(2-) clusters. Uncomplexed K atoms effectively cap the square bases of the monocapped square antiprismatic [Ge(9)](2-) clusters. The optical band gap of the title compound is 1.25 eV. The use of weaker sequestering agents in the isolation of Ge cluster anions from en solutions provides an additional handle in a controlled molecular route to preparing new low-dimensional Zintl phases.

Synthesis and structure of Ca(18)Li(5)In(25.07): a novel intergrowth of Li-centered in(12) icosahedral clusters and electron-precise Zintl layers.

A new ternary polar intermetallic, Ca(18)Li(5)In(25.07), was obtained from high-temperature reactions of the elements in welded Nb tubes. Its crystal structure, established by single-crystal X-ray diffraction, was found to crystallize in the orthorhombic space group Cmmm (No. 65). Unit cell parameters are a = 9.9151(6) A, b = 26.432(2) A, and c = 10.2116(6) A; Z = 2. The structure of Ca(18)Li(5)In(25.07) features two distinct types of indium anionic layers. An "electron-deficient" layer is made up of Li-centered In(12) icosahedra that are interconnected by bridging planar In(4) units and In atoms. A second In(3)(5-) layer is an electron-precise Zintl layer formed by fused four-, five-, and six-membered rings of three- and four-bonded indium atoms. The two distinct layers are alternately stacked and linked into a complex three-dimensional network. Vacancies are observed to occur only at the In(12) icosahedral and the bridging indium units within the "electron-deficient" layers. Magnetic property measurements indicate that Ca(18)Li(5)In(25.07) exhibits temperature-independent paramagnetism consistent with metallic behavior. Band structure calculations were performed to elucidate the role of defects and vacancies in the electronic structure of the electron-deficient "metallic" Zintl phase.

Nine hexagonal ca(5)pb(3)z phases in stuffed mn(5)si(3)-type structures with transition metal interstitial atoms z. Problems with classical valence States in possible zintl phases.

Ternary hexagonal Ae(5)Tt(3)Z phases have been obtained from high-temperature reactions (1000-1300 degrees C in Ta) only for Ae (alkaline-earth metal) = Ca, Tt (tetrel) = Pb, and Z = V, Cr, Mn, Fe, Co, Ni, Zn, Ru, or Cd. The hexagonal crystal structures (stuffed Mn(5)Si(3)-type, P6(3)/mcm, Z = 2) were refined for Z = Mn and Fe (a = 9.3580(3), 9.3554(5) A, c = 7.009(1), 7.009(1) A, respectively). In contrast, Ca(5)Pb(3)Z for Z = Cu or Ag form only with a trigonal structure (P3c1, Z = 2, a = 9.4130(3) A, c = 7.052(1) A for Cu) in which regular displacements of only the linear strings of Ca1 atoms occur. The existence of these compounds stands in contrast to the nonexistence of all binary Ae(5)Tt(3) products from Ca to Ba (Ae) and Si to Pb (Tt) with a Mn(5)Si(3)-type structure. Therefore, it once seemed attractive to consider the Z elements in these Ca(5)Pb(3)Z compounds as reducing agents (electron donors). The Mn and Fe structures appropriately exhibit greatly enlarged antiprismatic calcium cavities about Z. Other indications of relatively electron-poor environments around Fe are found in its properties, which include soft ferromagnetism with an elevated magnetic moment (6.3 micro(B)) and a large Fe 3p(3/2) binding energy relative to that in La(5)Ge(3)Fe, La(15)Ge(9)Fe, etc. The Ca(5)Pb(3)Mn phase exhibits metallic behavior (rho(295) = 135 microOmega cm) and temperature-independent Pauli paramagnetism. These properties are supported by ab initio band structure calculations for Ca(5)Pb(3)Mn, which show strong Ca-Pb bonding and a broad Pb-based band, with appreciable Ca-Mn and Ca-Pb bonding states at and above E(F). Distortion of the Cu analogue gives strengthened Ca-Pb bonding and reduced Cu-Ca1 repulsions. A Zintl phase description of these compounds and some related compounds in terms of closed Pb bands is not appropriate.

X-ray and neutron diffraction studies on "Li4.4Sn".

A chemical analysis and detailed structural characterization, using X-ray single crystal and neutron powder diffraction, of the binary lithium-tin compound "Li(4.4)Sn" is presented. Phase analyses and subsequent structural refinements result in the reformulation of "Li(4.4)Sn" as Li(17)Sn(4). The lithium-rich binary phase crystallizes with a complex cubic structure in the space group Ffourmacr;3m, with a = 19.6907(11) A, Z = 20. The improved crystal structure determination indicates well-defined lithium atom positions, some of which differ from those previously reported. The nearly Zintl phase Li(17)Sn(4) exhibits poor metallic behavior similar to that of heavily doped semiconductors. Comparisons of the refined crystal structure with previously reported X-ray crystal structures associated with "Li(4.4)Sn" are discussed.