Thioaluminogermanate M(AlS2)(GeS2)4 ( M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27Al and 23Na NMR Spectroscopy.

The new thioaluminogermanate Na(AlS2)(GeS2)4 (1) was successfully synthesized by a direct combination reaction. The compound crystallizes in the monoclinic space group P21/ n (no. 14) with unit cell parameters a = 6.803(3) Å, b = 38.207(2) Å, c = 6.947(4) Å, and ß = 119.17(3)°. The crystal structure is composed of a [(AlS2)(GeS2)4]- 3D polyanionic network, in which Al and Ge atoms share the atomic positions and Na cations occupy the channels and voids formed by the connection of (Ge/Al)S4 tetrahedra. The title compound shows a cation-exchange property with monovalent Ag+ and Cu+ ions at room temperature in solvent media, resulting in the formation of the isostructural compounds Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3), respectively. The ion-exchange products Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3) show higher air stability and narrower bandgap energies compared to those of the parent compound Na(AlS2)(GeS2)4 (1).

MAu2GeS4-Chalcogel (M = Co, Ni): Heterogeneous Intra- and Intermolecular Hydroamination Catalysts.

High surface area macroporous chalcogenide aerogels (chalcogels) MAu2GeS4 (M = Co, Ni) were prepared from K2Au2GeS4 precursor and Co(OAc)2 or NiCl2 by one-pot sol-gel metathesis reactions in aqueous media. The MAu2GeS4-chalcogels were screened for catalytic intramolecular hydroamination of 4-pentyn-1-amine substrate at different temperatures. 87% and 58% conversion was achieved at 100 °C, using CoAu2GeS4- and NiAu2GeS4-chalcogels respectively, and the reaction kinetics follows the first order. It was established that the catalytic performance of the aerogels is associated with the M2+ centers present in the structure. Intermolecular hydroamination of aniline with 1-R-4-ethynylbenzene (R = -H, -OCH3, -Br, -F) was carried out at 100 °C using CoAu2GeS4-chalcogel catalyst, due to its promising catalytic performance. The CoAu2GeS4-chalcogel regioselectively converted the pair of substrates to respective Markovnikov products, (E)-1-(4-R-phenyl)-N-phenylethan-1-imine, with 38% to 60% conversion.

SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions.

Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

Ion-exchangeable cobalt polysulfide chalcogel.

We present a promising approach in synthetic chalcogel chemistry that is extendable to a broad variety of inorganic spacers. Polychalcogenide aerogels with ion-exchange properties are demonstrated in cobalt polysulfide. The new materials show a broad range of pore sizes and high surface area of 483 m(2)/g.

Aluminosilicate relatives: Chalcogenoaluminogermanates Rb(3)(AlQ(2))(3)(GeQ(2))(7) (Q = S, Se).

The new compounds Rb(3)(AlQ(2))(3)(GeQ(2))(7) [Q = S (1), Se (2)] feature the 3D anionic open framework [(AlQ(2))(3)(GeQ(2))(7)](3-) in which aluminum and germanium share tetrahedral coordination sites. Rb ions are located in channels formed by the connection of 8, 10, and 16 (Ge/Al)S(4) tetrahedra. The isostructural sulfur and selenium derivatives crystallize in the space group P2(1)/c. 1: a = 6.7537(3) Å, b = 37.7825(19) Å, c = 6.7515(3) Å, and ß = 90.655(4)°. 2: a = 7.0580(5) Å, b = 39.419(2) Å, c = 7.0412(4) Å, ß = 90.360(5)°, and Z = 2 at 190(2) K. The band gaps of the congruently melting chalcogenogermanates are 3.1 eV (1) and 2.4 eV (2).

Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-.

The first discrete anionic indium thiophosphate complexes are reported. The structures of K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1), Rb(6)[In(PS(4))(PS(5))(2)] (2), and Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS(4)](3-) and the new [PS(5)](3-) ion. The conformation and bonding of the unsymmetric chelate ligand [PS(5)](3-) to indium give rise to different anions of the general formula [In(PS(4))(1+x)(PS(5))(2-x)](6-) (x = 0, 0.5). The anionic moiety in K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1) consists of cocrystallizing lambda-[In(PS(4))(2)(PS(5))](6-) and Lambdalambdadelta-[In(PS(4))(PS(5))(2)](6-) anions in a ratio of 1:1 (and their enantiomers). In Rb(6)[In(PS(4))(PS(5))(2)] (2), no cocrystallizatzion of anions was observed, and only the Lambdalambdalambda-[In(PS(4))(PS(5))(2)](6-) anion (and its enantiomer) is present. Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) shows the same disorder between [PS(4)](3-) and [PS(5)](3-) ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Lambdadeltadelta-[In(PS(4))(PS(5))(2)](6-) anion cocrystallizing with delta-[In(PS(4))(2)(PS(5))](6-). Additionally, ordered Rb(6)[In(PS(4))(PS(5))(2)] (2) was characterized by (31)P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.

Structural diversity by mixing chalcogen atoms in the chalcophosphate system K/In/P/Q (Q = S, Se).

The new thiophosphate salt K(4)In(2)(PS(4))(2)(P(2)S(6)) (1), the selenophosphate salts K(5)In(3)(mu(3)-Se)(P(2)Se(6))(3) (2), K(4)In(4)(mu-Se)(2)(P(2)Se(6))(3) (3), and the mixed seleno-/thiophosphate salt K(4)In(4)(mu-Se)(P(2)S(2.36)Se(3.64))(3) (4) are described. For the first time, a structurally different outcome of a chalcophosphate reaction was observed when sulfur and selenium are mixed, for example, by the use of K(2)S/P(2)Se(5)/S/In instead of K(2)Se/P(2)Se(5)/Se/In or K(2)S/P(2)S(5)/S/In. In compounds 1-4 indium atoms exist in a variety coordination environments. While in 1, indium is octahedrally coordinated, in 2-4 tetrahedral, trigonal-bipyramidal, and octahedral coordination environments are found for indium atoms. This remarkable structural diversity possibly is a reason, why particularly indium chalcophosphate flux reactions often produce a large variety of compounds at intermediate temperatures. In the mixed seleno-/thiophosphate salt K(4)In(4)(mu-Se)(P(2)S(2.36)Se(3.64))(3) (4) most of the chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy. There is, however, a preference for Se binding to In ions and S binding to potassium ions.

Soft-hard acid-base interactions: probing coordination preferences of sulfur and selenium in mixed chalcophosphates in the family APbPS(4-x)Se(x) (A = K, Rb, Cs; x = 0-4).

The synthesis and structures of the three new compounds, KPbPS(1.84)Se(2.16) (1), RbPbPS(1.56)Se(2.43) (2), and CsPbPS(3.46)Se(0.54) (3), are reported. The solid state structures of 1-3 consist of two-dimensional layers of [PbP(S/Se)(4)] separated by alkali metal ions. The structure of 1 was solved in the orthorhombic space group Pna2(1). Compounds 2 and 3 possess the CsSmGeS(4) structure type, crystallizing in the orthorhombic space group P2(1)2(1)2(1). All compounds were refined as racemic twins. All chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy; however, there is a preference for Se binding to Pb ions and S binding to alkali ions. A (31)P magic angle spinning NMR study on 1 suggests that, in mixed seleno-/thiophosphates, all of the anions [PS(x)Se(4-x)](3-) (x = 0, 1, 2, 3, 4) are present. The different amount of sulfur and selenium present in KPbPS(1.84)Se(2.16) (1), RbPbPS(1.56)Se(2.43) (2), and CsPbPS(3.46)Se(0.54) (3) is reflected in the solid state absorption spectra from which bandgaps of 2.2 eV were determined for 1 and 2, and a blue-shift to 2.5 eV was observed because of the higher sulfur-content in 3. Thermogravimetric analysis experiments indicated that, upon heating, compound 1 decomposes forming PbSe and sulfur together with other unidentified products. A Raman spectrum of compound 1 showed more bands than are usually observed in seleno- or thiophosphate salts and is another indicator of the mixed seleno-/thiophosphate anions found in 1.

A recipe for new organometallic polymers and oligomers? Synthesis and structure of an oligo- and a polymeric arrangement of P-S anions.

A route to organometallic polymers and oligomers is described using metal complexes with P/S-ligands as examples.

Crystal structure of hexa-kis-(dimethyl sulfoxide-κO)manganese(II) tetra-iodide.

The title salt, [Mn(C2H6OS)6]I4, is made up from discrete [Mn(DMSO)6]2+ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I42- tetra-iodide anions. The MnII ion in the cation, situated on a position with site symmetry -3., is octa-hedrally coordinated by O atoms of the DMSO mol-ecule with an Mn-O distance of 2.1808 (12) Å. The I42- anion contains a neutral I2 mol-ecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetra-iodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues.

Reactions of P/S-containing proligands with coinage metal salts: a new route to polynuclear complexes with unusual structural types.

The reactions of P/S-precursors with coinage metal alkoxides and carboxylates offer new perspectives for the synthesis of complex metal aggregates.

Crystal structure of tri-chlorido-(4'-ferrocenyl-2,2':6',2''-terpyridine-κ(3) N,N',N'')iridium(III) aceto-nitrile disolvate.

In the title compound, [FeIr(C5H5)(C20H14N3)Cl3]·2CH3CN, the central Ir(III) atom is sixfold coordinated by three chloride ligands and three terpyridine N atoms in a slightly distorted octa-hedral fashion. The terpyridine ligand is functionalized at the 4'-position with a ferrocenyl group, the latter being in an eclipsed conformation. In the crystal, mol-ecules are stacked in rows parallel to [001], with the aceto-nitrile solvent mol-ecules situated between the rows. An extensive network of intra- and inter-molecular C-H⋯Cl inter-actions is present, stabilizing the three-dimensional structure.

Tin(II) ketoacidoximates: synthesis, X-ray structures and processing to tin(II) oxide.

Tin(II) ketoacidoximates of the type [HON=CRCOO]2Sn (R = Me 1, CH2Ph 2) and (MeON=CMeCOO)3Sn](-) NH4(+)·2H2O 3 were synthesized by reacting pyruvate- and hydroxyl- or methoxylamine RONH2 (R = H, Me) with tin(II) chloride dihydrate SnCl2·2H2O. The single crystal X-ray structure reveals that the geometry at the Sn atom is trigonal bipyramidal in 1, 2 and trigonal pyramidal in 3. Inter- or intramolecular hydrogen bonding is observed in 1-3. Thermogravimetric (TG) analysis shows that the decomposition of 1-3 to SnO occurs at ca. 160 °C. The evolved gas analysis during TG indicates complete loss of the oximato ligand in one step for 1 whereas a small organic residue is additionally removed at temperatures >400 °C for 2. Above 140 °C, [HON=C(Me)COO]2Sn (1) decomposes in air to spherical SnO particles of size 10-500 nm. Spin coating of 1 on Si or a glass substrate followed by heating at 200 °C results in a uniform film of SnO. The band gap of the produced SnO film and nanomaterial was determined by diffuse reflectance spectroscopy to be in the range of 3.0-3.3 eV. X-ray photoelectron spectroscopy indicates surface oxidation of the SnO film to SnO2 in ambient atmosphere.

Solar cells. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals.

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3(+); X = Br(-) or I(-)) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 10(9) to 10(10) per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

Synthesis and properties of the metallo-supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO3: Ag+/Cu2+ ion exchange and effective antibacterial activity.

The commercial polymeric anhydride poly(methyl vinyl ether-alt-maleic anhydride) (PVM/MA) is converted by reaction with NaOH to give poly(methyl vinyl ether-alt-mono-sodium maleate) (PVM/Na-MA). By addition of AgNO3-solution, the formation of the silver(i) supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO3 is reported. Freeze-dried samples of the hydrogel show a mesoporous network of polycarboxylate ligands that are crosslinked by silver(i) cations. In the intact hydrogel, ion-exchange studies are reported and it is shown that Ag+ ions can be exchanged by copper(ii) cations without disintegration of the hydrogel. The silver(i) hydrogel shows effective antibacterial activity and potential application as burn wound dressing.

Reactivity of a heterocyclic As-Se compound with metal salts: syntheses and structures of the first copper complexes and of new alkali metal salts containing As-Se anions.

The structures of the new compounds [Cu8(Ph2As2Se2)2(PhAsSe2)2(dppm)4] (1) (dppm = bis-diphenylphosphinomethane), [Cu4(Ph2As2Se2)2(PPh3)4] (2), [{K(18-crown-6)}2(PhAsSe3)] (3), [Na12(PhAsSe3)6(15-crown-5)6] (4) and 1/x[Na2(PhAsSe3)(thf)(H2O)3]x (5) are reported. 2-5 were prepared by reactions of metal thiolates with [(PhAs)2(mu-Se)(mu-Se2)].

DFT modeling of silver disorder and mobility in the semiconductor cluster [Ag28S26(P(O)PhOMe)12(PPh3)12].

Disorder of silver atoms and high cation mobility are commonly observed and closely coupled features in silver chalcogenides. The ligand-stabilized cluster [Ag28(micro6-S)2{ArP(O)S2}12(PPh3)12] (1) (Ar=4-anisyl), with a total of 666 atoms, displays in its X-ray structure highly localized disorder at two core silver atoms. To explore the nature of this disorder, we have applied density functional methods to its internal structure and flexibility. The pseudo-S6 symmetry of the cluster provides six equivalent pockets to place the pair of silver atoms, and with the exception of populating neighboring sites, all permutations relax to structures with similar cores. The barrier to concerted motion of the central silver atoms from one set of pockets to the next of the Ci-symmetric conformer is estimated to be less than about 26 kJ mol(-1). Cluster 1 can be considered a model for bulk phase cation mobility.

Cleavage of P-S bonds and oxygenation by a trinuclear iron carboxylate: synthesis and structures of iron clusters containing group 15/16 anions.

The first reactions of the trinuclear oxygen-centred iron carboxylate [Fe(3)(mu(3)-O)(mu(2)-piv)(6)(H(2)O)(3)](piv) (piv=(t)BuCOO(-)) with the neutral ligand precursor [RP(S)(mu-S)](2) (R=4-anisyl) are reported.