Structure and Bonding in Cyclic Sulfur-Nitrogen Compounds—Molecular Orbital Considerations

The molecular structures of monocyclic sulfur-nitrogen ring systems, such as S₂N₂, S₃N, S₄N and S₅N, can be considered as examples of electron rich (4n + 2)π systems. The structures of S₄N₄, S₄N, P₄S₄, As₄S₄ and the bicyclic structures S₄N, S₄N as well as S₅N₆ can be rationalized on the basis of a planar tetrasulfur tetranitride with 12π electrons.     

2D‐Polymeric Anion Networks: The Two Novel Perselenoborates BaB2Se6 and Ba2B4Se13

Systematic investigations of ternary barium selenoborates led to the new compounds BaB₂Se₆ and Ba₂B₄Se₁₃ which represent the first alkaline earth perselenoborates. Appropriate amounts of barium selenide, boron and selenium were filled into carbon coated silica tubes which were sealed under vacuum. The high temperature reactions and subsequent annealing processes were performed in horizontal one‐zone furnaces. By means of single crystal X‐ray diffraction the structure of BaB₂Se₆ was determined to be orthorhombic, space group Cmca (no. 64) with a = 11.326(2)Å, b = 7.659(2)Å and c = 10.315(2)Å, while for Ba₂B₄Se₁₃ the monoclinic space group P2₁/c (no. 14) was found with a = 12.790(3)Å, b = 11.560(2)Å, c = 12.862(3)Å and β = 103.22(3)°. BaB₂Se₆ exhibits infinite layers of [B₂Se₆^2—]_∞‐anions oriented parallel to the a‐b‐plane. Each layer consists of B₂Se₂four‐membered rings, which are connected via four diselenide bridges. Thus, B₆Se₁₂‐rings are formed in which the barium cations are located. Likewise, in Ba₂B₄Se₁₃ polymeric [B₄Se₁₃^4—]_∞‐anions are running parallel to the a‐c‐plane resulting in a new layered structure type built of alternating B₂Se₄‐ and B₂Se₃‐rings which are connected by perseleno contacts.     

Syntheses and Crystal Structures of Rb2B2Se7, Tl2B2Se7, Cs3B3Se10, and Tl3B3Se10: New Perseleno‐selenoborates with Polymeric Anionic Chains

The perseleno‐selenoborates Rb₂B₂Se₇ and Cs₃B₃Se₁₀ were prepared from the metal selenides, amorphous boron and selenium, the thallium perseleno‐selenoborates Tl₂B₂Se₇ and Tl₃B₃Se₁₀ directly from the elements in evacuated carbon coated silica tubes by solid state reactions at temperatures between 920 K and 950 K. All structures were refined from single crystal X‐ray diffraction data. The isotypic perseleno‐selenoborates Rb₂B₂Se₇ and Tl₂B₂Se₇ crystallize in the monoclinic space group I 2/a (No. 15) with lattice parameters a = 12.414(3) Å, b = 7.314(2) Å, c = 14.092(3) Å, β = 107.30(3)°, and Z = 4 for Rb₂B₂Se₇ and a = 11.878(2) Å, b = 7.091(2) Å, c = 13.998(3) Å, β = 108.37(3)° with Z = 4 for Tl₂B₂Se₇. The isotypic perseleno‐selenoborates Cs₃B₃Se₁₀ and Tl₃B₃Se₁₀ crystallize in the triclinic space group P1 (Cs₃B₃Se₁₀: a = 7.583(2) Å, b = 8.464(2) Å, c = 15.276(3) Å, α = 107.03(3)°, β = 89.29(3)°, γ = 101.19(3)°, Z = 2, (non‐conventional setting); Tl₃B₃Se₁₀: a = 7.099(2) Å, b = 8.072(2) Å, c = 14.545(3) Å, α = 105.24(3)°, β = 95.82(3)°, γ = 92.79(3)°, and Z = 2). All crystal structures contain polymeric anionic chains of composition ([B₂Se₇]^2–)_n or ([B₃Se₁₀]^3–)_n formed by spirocyclically fused non‐planar five‐membered B₂Se₃ rings and six‐membered B₂Se₄ rings in a molar ratio of 1 : 1 or 2 : 1, respectively. All boron atoms have tetrahedral coordination with corner‐sharing BSe₄ tetrahedra additionally connected via Se–Se bridges. The cations are situated between three polymeric anionic chains leading to a nine‐fold coordination of the rubidium and thallium cations by selenium in M₂B₂Se₇ (M = Rb, Tl). Coordination numbers of Cs⁺ (Tl⁺) in Cs₃B₃Se₁₀ (Tl₃B₃Se₁₀) are 12(11) and 11(9).     

Microscopical Structuring of Solids by Molecular Beam Epitaxy—Spatially Resolved Materials Synthesis

Interfaces and heterojunctions which are incorporated into a crystal in well-defined geometrical and spatial arrangements can lead to a structuring or engineering of (semiconducting) solids down to atomic dimensions. The electrical and optical properties are then defined locally, and phenomena related to extremely small dimensions (“quantum size effects”) become more important than the actual chemical properties of the materials used. The technique of molecular beam epitaxy allows an atomic layer-by-layer deposition in a two-dimensional growth process, and crystalline materials in alternating layers of arbitrary composition and only a few atomic layers thickness are formed. The synthesis of microscopically structured solids by molecular beam epitaxy affords access to a new class of materials with accurately tailored electrical, optical, magnetic, dielectric, mechanical etc. properties. The semiconductor and metal superlattices described in this article, which are made of alternating thin layers of two different materials, symbolize just the beginning of a new area of materials engineering on a molecular (or atomic) scale. This periodic modulation of the chemical composition normal to the surface imposes an artificial periodicity on the semiconductor or metal crystal, a periodicity of one or two orders of magnitude larger than its natural lattice spacing. The synthesis of other materials combinations, including semiconductor/metal, semiconductor/insulator, metal/insulator, polymers, and magnetic materials, with entirely different properties and for completely different applications will certainly follow. Finally, a large variety of desired combinations of elements can be selected, and even metastable compounds with novel exciting properties can be synthesized by molecular beam epitaxy.     

Novel High-Performance Ceramics—Amorphous Inorganic Networks from Molecular Precursors

Materials research is an interdisciplinary field in which engineers and physical scientists work together. Since the major binary oxides, nitrides, and carbides, which are currently used as high-performance ceramics, were discovered in the last century, the role of chemistry in the development of materials has become barely noticeable. This has changed only in the recent past as, for example, purity and defined morphology of starting powders were recognized as crucial parameters for enhancing the reliability of ceramic workpieces. While the application of chemical methods led to gradual–though significant–improvements, the true potential of chemistry lies rather in the exploitation of new chemical systems and the development of new preparative routes to already known materials. Such an approach is the preparation of ceramics from molecular or polymeric precursors. Herein we survey the most important contributions to those preparative routes starting from the pioneering work in the 1960s and the 1970s; a certain emphasis is placed on the concepts that we have applied to the preparation of multinary, nonoxide materials and amorphous inorganic networks. The name “amorphous high-performance ceramics” is in fact a contradiction in terms. Such materials are thermodynamically unstable with respect to the transformation or decomposition to crystalline phases, thus excluding their application in sensitive areas at high temperatures. However, the selection of element combinations for which the binding energies are derived from strong, local covalent bonds and which are therefore less dependent on a long-range crystalline order, can yield amorphous materials of remarkable thermal and mechanical durability. This is exemplified by novel quaternary ceramics in the Si/B/N/C system, for which an efficient synthesis, starting from raw materials suitable for industrial production, has been developed. For instance, a material of the composition SiBN₃C remains amorphous up to 1900°C, which is unique, and, with respect to oxidation, is the most stable nonoxide ceramic known to date. Another advantage of this in several respects unsurpassed material is the simple way, in which the viscosity of the polymeric precursors can be adjusted to various methods of shaping. So far infiltrations and coatings have been realized. Most developed is the preparation of fibers, which in terms of their performance characteristics are significantly better than those currently available.     

New Forms and Functions of Tellurium: From Polycations to Metal Halide Tellurides

Metal chalcogenides and metal chalcogenide halides are distinguished by their structural diversity and by their very different physical properties. Therefore, the synthesis of novel compounds from this class is always a rewarding goal for the preparatively oriented solid-state chemist. Over the past few years, many syntheses and structural investigations have stimulated the field. The emphasis of the research has been placed on selenium-rich and tellurium-rich compounds, which are characterized by directed covalent bonds between the chalcogen atoms. Compounds with novel chalcogen polycations have also become accessible during the past few years by reacting the chalcogen elements with transition metal halides, or from chemical vapor deposition in the sense of chemical transport reactions. In these compounds, tellurium differs from its lighter homologues by a pronounced tendency towards greater covalence. This article attmepts to provide an overview of new developments in the field of compounds with chalcogen polycations and of metal chalcogenide halides, with an emphasis on compounds containing molybdenum and tungsten as the transition metals and tellurium as the chalcogen.     

The Valence States of Nickel,Tin, and Sulfur in the Ternary Chalcogenide Ni3Sn2S2—XPS, 61Ni and 119Sn Mössbauer Investigations,and Band Structure Calculations

The hitherto controversial valence states of nickel and tin in the ternary chalcogenide Ni₃Sn₂S₂ (see structure) have been determined by photoelectron and Mössbauer spectroscopy (⁶¹Ni, ¹¹⁹Sn). Results from band structure calculations confirmed that this shandite phase is a metal and that the approximate distribution of the valence electrons is (Ni⁰)₃(Sn(1)^II)(Sn(2)^II)(S^II−)₂.     

A comparison of the solid-state structures of a series of phenylseleno-halogen and pseudohalogen compounds,PhSeX (X = Cl,CN, SCN)

Structural and spectroscopic data on the series of compounds “PhSeX”, where X = Cl, CN or SCN, are reported and compared with previously reported data on “PhSeX” systems (X = Br and I). The chloro-compound displays a “square” motif, Ph₄Se₄Cl₄, in the solid state, linked by long Se–Se bonds [2.993(3)–3.035(3) Å], and forms a loosely held network of Se₄ and Cl₄ squares in its extended structure. In contrast, the pseudohalogen derivatives, PhSeCN and PhSeSCN, consist of essentially monomeric units, which form chains held together by weak Se?N interactions in the solid state. These Se?N interactions are much shorter in PhSeCN, 3.023(3)–3.065(4) Å, than in PhSeSCN, 3.348(4) Å. Weaker Se?N contacts are also present between the chains. The structure of PhSeSCN described here is the first reported crystallographic study of a selenium thiocyanate compound. Spectroscopic studies suggest that all three compounds exist as monomers in solution. The results reported herein illustrate the subtle differences in the solid-state structures of PhSeX compounds.     

Sulfur Spillover on Carbon Materials and Possible Impacts on Metal–Sulfur Batteries

There is currently intense research on sulfur/carbon composite materials as positive electrodes for rechargeable batteries. Such composites are commonly prepared by ball milling or (melt/solution) impregnation to achieve intimate contact between both elements with the hope to improve battery performance. Herein, we report that sulfur shows an unexpected “spillover” effect when in contact with porous carbon materials under ambient conditions. When sulfur and porous carbon are gently mixed in a 1:1 mass ratio, complete surface coverage takes place within just a few days along with the loss of the sulfur bulk properties (crystallinity, melting point, Raman signals). Sulfur spillover also occurs in the presence of a liquid phase. Consequences of this phenomenon are discussed by considering a sodium–sulfur cell with a solid electrolyte membrane.     

Thio- and Seleno-Compounds of Main Group Elements—Novel Inorganic Oligomers and Polymers

During the last decade modern preparative and structural methods have led to novel and often unexpected oligomeric and polymeric main group element-sulfur compounds having remarkable bonding and structural properties and reactivities. Examples of important new developments in this area are: the discovery of boron sulfides B₈S₁₆ and (BS₂)_n and of ion-conducting air-stable thioborates with tetrahedrally coordinated boron; the successful use of boron sulfides in organic and inorganic syntheses; the preparation of different homologous series of molecular polynuclear thio- and selenoanions of Ga, In, Si, Ge and Sn, and of new polynuclear sulfide- and selenide-halides of Si and Ge as interesting reagents for inorganic and organic reactions; the synthesis of argyrodite(Ag₈GeS₆)-like phases with remarkable solid-state properties; and the characterization of the S? H…S type hydrogen bridge in thiocarbonic acid and thiophosphinic acids, which is of importance for an understanding of certain interactions in sulfur-containing biomolecules.     

Synthesis and Crystal Structure of {(NH4)xCo((3–x)/2)}(H2O)2[BP2O8] · (1 – x) H2O (x ≈ 0.5)

A borophosphate hydrate with general composition {(NH₄)_xCo_((3–x)/2)}(H₂O)₂[BP₂O₈] · (1 – x) H₂O (x ≈ 0.5) was prepared under mild hydrothermal conditions (T = 170 °C). The crystal structure of the purple title compound was refined in space group P6₅ (no. 170) as a merohedric twin (a = 949.14 pm, c = 1558.25 pm, R₁ = 0.037, wR₂ = 0.092 for all data). According to preliminary X‐ray investigations, vis‐spectra, and magnetic susceptibility measurements, a second blue coloured variant exhibits a superstructure of the title compound with a change in coordination numbers around cobalt from six and five to six and four. Both phases show reversible de‐/rehydration properties.     

Synthesis and Crystal Structure of δ-GeS2, the First Germanium Sulfide with an Expanded Framework Structure

Polycondensation of molecular adamantanoid [Ge₄S₁₀]⁴⁻ precursors at a remarkably low temperature (50°C) affords the crystalline binary dichalcogenide δ-GeS₂. Its crystal structure contains two interpenetrating cristobalite-like frameworks composed of adamantanoid [Ge₄S₆S_4/2] building blocks. Rings containing 24 atoms form the largest pores of each network (shown on the right).     

Self‐Assembled Selenium Monolayers: From Nanotechnology to Materials Science and Adaptive Catalysis

Self‐assembled monolayers (SAMs) of selenium have emerged into a rapidly developing field of nanotechnology with several promising opportunities in materials chemistry and catalysis. Comparison between sulfur‐based self‐assembled monolayers and newly developed selenium‐based monolayers reveal outstanding complimentary features on surface chemistry and highlighted the key role of the headgroup element. Diverse structural properties and reactivity of organosulfur and organoselenium groups on the surface provide flexible frameworks to create new generations of materials and adaptive catalysts with unprecedented selectivity. Important practical utility of adaptive catalytic systems deals with development of sustainable technologies and industrial processes based on natural resources. Independent development of nanotechnology, materials science and catalysis has led to the discovery of common fundamental principles of the surface chemistry of chalcogen compounds.     

Combinatorial Chemistry—Challenge and Chance for the Development of New Catalysts and Materials

One should not underestimate the capability of the combinatorial method in solid-state chemistry; this is the opinion of the author. Combinatorial chemistry can provide a large number of new compounds, but once the components that are interesting for a certain application have been successfully selected, the techniques of conventional catalysis and materials research are required. The strengths of conventional chemistry lie in the optimization, systematic modification, and improvement of new lead structures. In contrast, discovery is the potential strength of combinatorial chemistry. Careful design is most important for the synthesis of useful libraries, since the diversity of the periodic table is much too large to be accessed comprehensively or systematically by such large libraries.     

Sol‐Gel‐Process in the Ammono‐System – a Novel Access to Silicon Based Nitrides

Controlled coammonolysis of elementalkylamides in aprotic organic solvents at low temperatures have been shown to result in the formation of polyazanes. The synthetic procedure developed may be addressed as “sol‐gel‐route in the ammono system”. Pyrolysis of these novel polymer precursors gave access to multinary nitrides. For the model systems Si(NHMe)₄/B(NMe₂)₃, Si(NHMe)₄/Ti(NMe₂)₄, and Si(NHMe)₄/Ta(NMe₂)₅ polymeric boro‐, titano and tantalosilazanes were obtained. Pyrolysis in ammonia at 1000 °C yielded amorphous silicon boron nitride, silicon titanium nitride and silicon tantalum nitride powders; further heating of the nitride powders at 1500 °C in nitrogen atmosphere led to the formation of partly crystalline composites of α‐Si₃N₄ and amorphous silicon boron nitride for the Si/B/N system, a composite of finely dispersed TiN and amorphous silicon titanium nitride for the Si/Ti/N system, and crystalline TaN and amorphous silicon nitride for the Si/Ta/N system. Furthermore, the structure and pyrolysis chemistry of the polymeric intermediates, as well as the morphology of the pyrolysis products, were studied by NMR, MAS‐NMR, FT‐IR, DTA‐TG‐MS, XRD, SEM, EDX and elemental analyses.     

An Alternative Method for the Preparation of Diphenylboron Chelates. The Crystal and Molecular Structures of (Pyridine‐2‐acetyloximato)diphenylboron and (1‐Phenylazo‐2‐naphtholato)diphenylboron

A convenient method for the preparation of diphenylboron chelates from ammonium tetraphenylborate is described. A variety of five‐ or six‐membered O,O‐, N,O‐ and N,N‐chelates were obtained in yields from 60 to 90 %. The isolated compounds were characterized by elemental analysis, IR spectroscopy and multinuclear magnetic resonance spectroscopy (¹H, ¹³C, and ¹¹B). The crystal and molecular structures of (pyridine‐2‐acetyloximato)diphenylboron and (1‐phenylazo‐2‐naphtholato)diphenylboron were determined by X‐ray diffraction on single crystals.     

Lithium–Sulfur Batteries: Electrochemistry,Materials, and Prospects

With the increasing demand for efficient and economic energy storage, Li‐S batteries have become attractive candidates for the next‐generation high‐energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li‐S batteries, this Review introduces the electrochemistry of Li‐S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li‐S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li‐S batteries with a metallic Li‐free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li‐S batteries serves as a prospective strategy for the industry in the future.