The Divalent Lanthanoid Triflates Ln(CF3SO3)2(CH3CN) (Ln=Sm, Eu): Structure, Luminescence, and Magnetism.

The reaction of the trivalent lanthanoide triflates Ln(OTf)3 (Ln=Sm, Eu; OTf=CF3SO3 -) with the respective metals in acetonitrile leads to the Ln(II)-triflates Eu(OTf)2(CH3CN) (monoclinic, P21/n, Z=4, a=1053.54(1), b=610.28(5), c=1946.92(2) pm, ß =98.611(4)) and Sm(OTf)2(CH3CN) (monoclinic, P21/n, Z=4, a=1054.41(4), b=612.16(2), c=1952.65(7) pm, ß =98.524(2)). The isotypic strontium compound Sr(OTf)2(CH3CN) (monoclinic, P21/n, Z=4, a=1056.39(5), b=610.05(3), c=1950.1(1) pm, ß =98.900(2)°) has been obtained from SrCO3 and triflic acid. The compounds have been investigated by X-ray diffraction, vibrational spectroscopy, luminescence spectroscopy, cyclic voltammetry, thermal analysis, and magnetic measurements.

Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and Pr2Si7O18.

The reaction between PrO2 and SiO2 was investigated at various pressure points up to 29 GPa in a diamond anvil cell using laser heating and in situ single-crystal structure analysis. The pressure points at 5 and 10 GPa produced Pr2III(Si2O7), whereas Pr4IIISi3O12 and Pr2IV(O2)O3 were obtained at 15 GPa. Pr4IIISi3O12 can be interpreted as a high-pressure modification of the still unknown orthosilicate Pr4III(SiO4)3. PrIVSi3O8 and Pr2IVSi7O18 that contain praseodymium in its rare + IV oxidation state were identified at 29 GPa. After the pressure was released from the reaction chamber, the Pr(IV) silicates could be recovered, indicating that they are metastable at ambient pressure. Density functional theory calculations of the electronic structure corroborate the oxidation state of praseodymium in both PrIVSi3O8 and Pr2IVSi7O18. Both silicates are the first structurally characterized representatives of Pr4+-containing salts with oxoanions. All three silicates contain condensed networks of [SiO6] octahedra which is unprecedented in the rich chemistry of lanthanoid silicates.

Impact of 1,10-Phenanthroline-Induced Intermediate Valence on the Luminesence of Divalent Europium Halides.

Starting from EuX2 (X = Cl, Br, I), we systematically investigated a variety of divalent europium complexes containing bidentate 1,10-phenanthroline (Phen) ligands. Depending on the Eu/Phen ratio, mono-, di-, and polynuclear complexes are formed, with the latter yielding one-dimensional ∞1[EuBr2(phen)] chains. Seven new divalent europium complexes, [Eu(phen)4(H2O)]Br2·2MeCN, [Eu(phen)4]I2·1.7Tol, [EuBr(phen)3]2Br2·4MeCN, [EuCl2(phen)2]2·2MeCN, [EuBr2(phen)2]2, [EuI2(phen)2]2, and [EuBr2(phen)]x, are presented in this work. All species show remarkable optical properties based on a partial electron transfer from the EuII center to the Phen ligand. The photophysical characterization is further supported by electrochemistry studies in order to describe the intermediate valence of the Eu center.

Determination of Cleavage Energy and Efficient Nanostructuring of Layered Materials by Atomic Force Microscopy.

A method is presented to use atomic force microscopy to measure the cleavage energy of van der Waals materials and similar quasi-two-dimensional materials. The cleavage energy of graphite is measured to be 0.36 J/m2, in good agreement with literature data. The same method yields a cleavage energy of 0.6 J/m2 for MoS2 as a representative of the dichalcogenides. In the case of the weak topological insulator Bi14Rh3I9 no cleavage energy is obtained, although cleavage is successful with an adapted approach. The cleavage energies of these materials are evaluated by means of density-functional calculations and literature data. This further validates the presented method and sets an upper limit of about 0.7 J/m2 to the cleavage energy that can be measured by the present setup. In addition, this method can be used as a tool for manipulating exfoliated flakes, prior to or after contacting, which may open a new route for the fabrication of nanostructures.

Polycations Stabilised by Borosulfates: [Au3 Cl4 ][B(S2 O7 )2 ] and the One-Dimensional Metal [Au2 Cl4 ][B(S2 O7 )2 ](SO3 ).

(SO4 )-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au3 Cl4 ][B(S2 O7 )2 ] and [Au2 Cl4 ][B(S2 O7 )2 ](SO3 ) were obtained by solvothermal reaction with SO3 , and the electronic properties were investigated by means of density functional theory-based calculations. [Au3 Cl4 ][B(S2 O7 )2 ] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au2 Cl4 ][B(S2 O7 )2 ](SO3 ) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.

Selenous Acid in an Aromatic Framework: Insights Into a Temperature-Sensitive Internal Redox System from the Solid State.

We report on a new compound composed of a phenanthroline network in which emerging channels are alternately occupied by selenous acid (H2SeO3) and dioxane molecules. The material undergoes a variety of structural changes due to both its redox activity as well as its thermal decomposition. We investigate an internal redox system of the incorporated selenous acid and the aldehyde groups of the phenanthroline framework. The reduction process of the selenium species was further elucidated by cyclic voltammetry, while the oxidation process was also monitored by 1H NMR spectra. The thermal behavior reveals that the material can undergo a reversible, topotactic transition due to dioxane and water (de)intercalation.

Acoustic cavitation generates molecular mercury(ii) hydroxide, Hg(OH)2, from biphasic water/mercury mixtures.

Emulsification of elemental mercury in aqueous solution in the form of grey particles occurs upon exposure to intense sound fields. We show the concomitant formation of molecular Hg(OH)2 in the solution phase reaching a saturation limit of 0.24 mM at 25 °C. The formation of Hg(OH)2 is consistent with the 'hot spot' model which suggests the formation of OH˙ as a result of acoustic cavitation; such radicals are proposed to combine with Hg to form the Hg(OH)2 species here characterised using voltammetry.

Introducing "Insertive Stripping Voltammetry": Electrochemical Determination of Sodium Ions Using an Iron(III) Phosphate-Modified Electrode.

A new type of stripping voltammetry is introduced, in which the preconcentration step includes ion insertion into a solid phase followed by a quantification step in which the ion is expelled via linear sweep voltammetry. Specifically, sodium-ion concentrations in both aqueous solution and synthetic sweat are electrochemically determined using iron(III) phosphate-modified glassy carbon electrodes. The electrochemical method consists of a potentiostatic step, holding the potential of -0.5 V vs saturated calomel electrode (SCE) for 100 s, followed by linear sweep voltammetry. It is shown that a thermal and mechanical pretreatment at 800 °C and with a ball mill, respectively, improve the electrochemical response of the iron(III) phosphate toward Na+. The involved structural and morphological changes were assessed by thermogravimetric analysis, scanning electron microscopy, and powder X-ray diffraction. The sensor exhibits a good selectivity toward Li+ and K+ and shows a linear response between 0.025 and 0.2 M Na+. As a proof-of-principle, the sensor was used to determine the sodium level in synthetic sweat.

Electrochemical Detection and Quantification of Lithium Ions in Authentic Human Saliva Using LiMn2O4-Modified Electrodes.

We report an electrochemical sensor for the detection of lithium ions (Li+) in authentic human saliva at lithium manganese oxide (LiMn2O4)-modified glassy carbon electrodes (LMO-GCEs) and screen-printed electrodes (LMO-SPEs). The sensing strategy is based on an initial galvanostatic delithiation of LMO followed by linear stripping voltammetry (LSV) to detect the reinsertion of Li+ in the analyte. The process was investigated using powder X-ray diffraction and voltammetry. LSV measurements reveal a measurable lower limit of 50.0 µM in both LiClO4 aqueous solutions and synthetic saliva samples, demonstrating the applicability of the proposed analytical method down to low Li+ concentrations. Four different samples of authentic human saliva were then analyzed with the established sensing strategy using LMO-SPEs, showing good linearity over a concentration range up to 5.0 mM Li+ with high reproducibility (RSD < 7%) and applicability for routine monitoring purposes. The total time needed to analyze a sample is less than 3 min.

In-situ Electrochemical X-ray Diffraction: A Rigorous Method to Navigate within Phase Diagrams Reveals ß-Fe1+x Se as Superconductor for All x.

We report the precise postsynthetic control of the composition of ß-Fe1+x Se by electrochemistry with simultaneous tracking of the associated structural changes via in situ synchrotron X-ray diffraction. We access the full phase width of 0.01

High-Temperature-Phase Bi4RhI2: Electronic Localization by Structural Distortion.

The metal-rich compound Bi4RhI2 was discovered in a thorough investigation of the Bi-Rh-I phase system. The monoclinic crystal structure was solved via single-crystal X-ray diffraction. It consists of infinite strands of face-sharing distorted square antiprisms ∞1[RhBi8/2]2+, which are separated by iodide ions. Bi4RhI2 is the high-temperature phase related to the weak three-dimensional topological insulator Bi14Rh3I9 (Bi4.67RhI3) and forms peritectically at 441 °C, where Bi14Rh3I9 decomposes. The structure of Bi4RhI2 is compared with Bi4RuI2 and Bi9Rh2I3, all three sharing a similar intermetallic strand-like structure, although their overall count of valence electrons differs. A chemical bonding analysis of Bi4RhI2 via the electron localizability indicator reveals a complex bonding pattern with covalent bonds between rhodium and bismuth, as well as between bismuth atoms and suggests a possible explanation for the formation of this structure type. Band structure calculations indicate a narrow band gap of 157 meV, which was verified by resistivity measurements on a pressed powder pellet and on single crystals. In a broader context, this strandlike structure type accounts for unusual physical phenomena, such as the transition into a charge-density-wave phase.

Electronic Structure of the Dark Surface of the Weak Topological Insulator Bi14Rh3I9.

Compound Bi14Rh3I9 consists of ionic stacks of intermetallic [(Bi4Rh)3I](2+) and insulating [Bi2I8](2-) layers and has been identified to be a weak topological insulator. Scanning tunneling microscopy revealed the robust edge states at all step edges of the cationic layer as a topological fingerprint. However, these edge states are found 0.25 eV below the Fermi level, which is an obstacle for transport experiments. Here, we address this obstacle by comparing results of density functional slab calculations with scanning tunneling spectroscopy and angle-resolved photoemission spectroscopy. We show that the n-type doping of the intermetallic layer is intrinsically caused by the polar surface and is well-screened toward the bulk. In contrast, the anionic "spacer" layer shows a gap at the Fermi level, both on the surface and in the bulk; that is, it is not surface-doped due to iodine desorption. The well-screened surface dipole implies that a buried edge state, probably already below a single spacer layer, is located at the Fermi level. Consequently, a multilayer step covered by a spacer layer could provide access to the transport properties of the topological edge states. In addition, we find a lateral electronic modulation of the topologically nontrivial surface layer, which is traced back to the coupling with the underlying zigzag chain structure of the spacer layer.

Correlation between topological band character and chemical bonding in a Bi14Rh3I9-based family of insulators.

Recently the presence of topologically protected edge-states in Bi14Rh3I9 was confirmed by scanning tunnelling microscopy consolidating this compound as a weak 3D topological insulator (TI). Here, we present a density-functional-theory-based study on a family of TIs derived from the Bi14Rh3I9 parent structure via substitution of Ru, Pd, Os, Ir and Pt for Rh. Comparative analysis of the band-structures throughout the entire series is done by means of a unified minimalistic tight-binding model that evinces strong similarity between the quantum-spin-Hall (QSH) layer in Bi14Rh3I9 and graphene in terms of Pz-molecular orbitals. Topologically non-trivial energy gaps are found for the Ir-, Rh-, Pt- and Pd-based systems, whereas the Os- and Ru-systems remain trivial. Furthermore, the energy position of the metal d-band centre is identified as the parameter which governs the evolution of the topological character of the band structure through the whole family of TIs. The d-band position is shown to correlate with the chemical bonding within the QSH layers, thus revealing how the chemical nature of the constituents affects the topological band character.

Low-temperature topochemical transformation of Bi13Pt3I7 into the new layered honeycomb metal Bi12Pt3I5.

Ordered single-crystals of the metallic subiodide Bi13 Pt3 I7 were grown and treated with n-butyllithium. At 45 °C, complete pseudomorphosis to Bi12 Pt3 I5 was achieved within two days. The new compound is air-stable and contains the same ${{{\hfill 2\atop \hfill \infty }}}$[(PtBi8/2 )3 I](n+) honeycomb nets and iodide layers as the starting material Bi13 Pt3 I7 , but does not include ${{{\hfill 1\atop \hfill \infty }}}$[BiI2 I4/2 ](-) iodidobismuthate strands. Electron microscopy and X-ray diffraction studies of solid intermediates visualize the process of the topochemical crystal-to-crystal transformation. In the electronic band structures of Bi13 Pt3 I7 and Bi12 Pt3 I5 , the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi13 Pt3 I7 into Bi12 Pt3 I5 , the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi13 Pt3 I7 the intermetallic layers do not interact across the iodidobismuthate spacers (two-dimensional metal), they couple in Bi12 Pt3 I5 and form a three-dimensional metal.

A metallic room-temperature oxide ion conductor.

Nanoparticles of Bi3 Ir, obtained from a microwave-assisted polyol process, activate molecular oxygen from air at room temperature and reversibly intercalate it as oxide ions. The closely related structures of Bi3 Ir and Bi3 IrOx (x≤2) were investigated by X-ray diffraction, electron microscopy, and quantum-chemical modeling. In the topochemically formed metallic suboxide, the intermetallic building units are fully preserved. Time- and temperature-dependent monitoring of the oxygen uptake in an oxygen-filled chamber shows that the activation energy for oxide diffusion (84 meV) is one order of magnitude smaller than that in any known material. Bi3 IrOx is the first metallic oxide ion conductor and also the first that operates at room temperature.

The topochemical pseudomorphosis of a chloride into a bismuthide.

The heterogeneous reaction of crystals of the novel intermetallic subhalide Bi12 Rh3 Cl2 with a solution of n-butyllithium at 70 °C led to the complete topochemical exchange of chloride ions for bismuth atoms, that is, the transformation into the isostructural metastable intermetallic superconductor Bi14 Rh3. The crystals underwent the reductive pseudomorphosis almost unchanged except some fissures perpendicular to the a-axis. Detailed inspections of the transformed crystals by electron microscopy indicated no volume defects that would indicate internal chemical reactions. Thus, extensive mass transport must have occurred through the seemingly dense crystal structure. An efficient transport mechanism, based on an unusual breathing mode of the three-dimensional network formed by edge-sharing [RhBi8 ] cubes and antiprisms, is proposed. The replacement of ionic interaction in the chloride by metallic bonding in the binary intermetallic compound closes the pseudo gap in the density of states at the Fermi level. As a result, the rod-packing of conducting, yet electrically isolated strands of [RhBi8] cubes in Bi12 Rh3 Cl2 turns into the three-dimensional metal Bi14 Rh3.

Stacked topological insulator built from bismuth-based graphene sheet analogues.

Commonly, materials are classified as either electrical conductors or insulators. The theoretical discovery of topological insulators has fundamentally challenged this dichotomy. In a topological insulator, the spin-orbit interaction generates a non-trivial topology of the electronic band structure dictating that its bulk is perfectly insulating, whereas its surface is fully conducting. The first topological insulator candidate material put forward--graphene--is of limited practical use because its weak spin-orbit interactions produce a bandgap of ~0.01 K. Recent reexaminations of Bi2Se3 and Bi2Te3, however, have firmly categorized these materials as strong three-dimensional topological insulators. We have synthesized the first bulk material belonging to an entirely different, weak, topological class, built from stacks of two-dimensional topological insulators: Bi14Rh3I9. Its Bi-Rh sheets are graphene analogues, but with a honeycomb net composed of RhBi8 cubes rather than carbon atoms. The strong bismuth-related spin-orbit interaction renders each graphene-like layer a topological insulator with a 2,400 K bandgap.