Structures, Bonding Analyses and Reactivity of a Dicationic Digallene and Diindene Mimicking trans-bent Ditetrylenes.

The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent M sources [M (PhF) ][pf] (M=Ga , In ; [pf] =[Al(OR ) ] ; R =C(CF ) ) yielded the salts [{M(dcpe)} ][pf] , containing the first dicationic, trans-bent digallene and diindene structures reported so far. The non-classical M ⇆M double bonds are surprisingly short and display a ditetrylene-like structure. The bonding situation was extensively analyzed by quantum chemical calculations, QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence) analyses and is compared to that in the isoelectronic and isostructural, but neutral digermenes and distannenes.

Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts.

The open-shell iron pentacarbonyl cation [Fe(CO) ] was isolated by deelectronation, i.e., the single-electron oxidation of the parent neutral Fe(CO) using [phenazine ] as the [Al(OR ) ] and [F-{Al(OR ) } ] salt (R =C(CF ) ; phenazine =perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine).

The tin sulfates Sn(SO) and Sn2(SO4)3: crystal structures, optical and thermal properties.

We report the crystal structures of two tin(IV) sulfate polymorphs Sn(SO4)2-I (2/ (no. 14), = 504.34(3), = 1065.

From 1D to 3D: Perovskites within the System HSC(NH)I/CHNHI/PbI with Maintenance of the Cubic Closest Packing.

This work describes crystalline phases of the system [HSC(NH)]I/(CHNH)I/PbI and discusses the crystal structures in the context of a common cubic closest packing of organic cations and iodide anions with Pb in all anionic octahedral voids. Ternary boundary phases were (CHNH)PbI (3D perovskite), [HSC(NH)]PbI (1D perovskite), [HSC(NH)]PbI (NHCdCl type), and [HSC(NH)]PbI, with strands of edge-sharing octahedra of the NHCdCl type, which are connected to 2D layers via common corners. Within the system, we identified ribbonlike structures of the general composition [HSC(NH)](CHNH)PbI with = 2 and 3, representing the transition from 1D to 2D structures.

Borosulfates-Synthesis and Structural Chemistry of Silicate Analogue Compounds.

Borosulfates are oxoanionic compounds consisting of condensed sulfur- and boron-centered tetrahedra. Hitherto, they were mostly achieved from solvothermal syntheses in SO -enriched sulfuric acid, or from reactions with the superacid H[B(HSO ) ]. The crystal structures are very similar to those of the corresponding class of silicates and their substitution variants, especially regarding the typical structural motif of corner-sharing tetrahedra.

Going Homoleptic: Synthesis and Full Characterization of Stable Manganese Tetranitrosyl Cation Salts.

Although similar to carbon monoxide, the chemistry of homoleptic nitrogen monoxide complexes is fundamentally unexplored compared to their carbonyl analogues. Herein we report the synthesis of the first truly homoleptic transition-metal nitrosyl cation as the salt of the weakly coordinating anions (WCAs) [Al(OR ) ] and [F{Al(OR ) } ] (R =C(CF ) ). These salts are easily accessible in good yields, phase pure, and were fully characterized by IR/Raman, NMR and UV/Vis spectroscopy as well as single-crystal and powder X-ray diffraction.

Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue.

Homoleptic carbonyl radical cations are a textbook family of complexes hitherto unknown in the condensed phase, leaving their properties and applications fundamentally unexplored. Here we report on two stable 17-electron [Cr(CO)] salts that were synthesized by oxidation of Cr(CO) with [NO][Al(OR)] (R = C(CF))) in CHCl and with removal of NO gas. Longer reaction times led to NO/CO ligand exchange and formation of the thermodynamically more stable 18-electron species [Cr(CO)(NO)], which belongs to the family of heteroleptic chromium carbonyl/nitrosyl cations.

Tailoring the Band Gap in 3D Hybrid Perovskites by Substitution of the Organic Cations: (CH NH ) (NH (CH ) NH ) Pb I (0≤y≤0.25).

Tuning the optical properties of MAPbI (MA=methylammonium) is a key requirement to increase the efficiency of perovskite solar cells (PSCs). Simple precipitation from solution allows the partial substitution of MA in MAPbI by H NCH CH NH (H en). Surprisingly, there is 1:1 exchange of the monovalent cation MA by the dication H en.

Synthesis, Crystal Structure, and Properties of Bi TeBO or Bi (TeO )(BO ): A Non-Centrosymmetric Borate-Tellurate(VI) of Bismuth.

Pale-yellow single crystals of the new borate tellurate(VI) Bi TeBO were obtained by reaction of stoichiometric amounts of Bi O , B O , and Te(OH) at 780 °C. The non-centrosymmetric crystal structure (P6 , Z=2, a=8.7454(16), c=5.

Synthesis, single-crystal structure and characterization of (CH3 NH3 )2 Pb(SCN)2 I2.

The perovskite phase (CH3 NH3 )2 Pb(SCN)2 I2 with a structure closely related to the K2 NiF4 -type was identified as the product of the reaction of CH3 NH3 I and Pb(SCN)2 by single-crystal X-ray analysis. This extends the range of suitable dyes for solar cell applications to a class of perovskite-related structures of the general composition (AMX3 )n (AX)m .

Synthesis, crystal structure, and spectroscopy of the mixed-valent boroseleniteselenate B2Se3O10.

The first mixed-valent boroseleniteselenate B2Se3O10 was obtained as a colorless, hygroscopic compound from the reaction of boric acid (H3BO3) in concentrated selenic acid (H2SeO4) at 265 °C. H2SeO4 can be replaced by appropriate amounts of SeO2 and H2O2. The crystal structure was determined from single-crystal data (P21/c, Z = 4, a = 4.

The first boroselenates as new silicate analogues.

The first boroselenates were obtained as single crystals by the reaction of selenic acid with boron acid and the corresponding alkali carbonates. The structure determinations showed a far-reaching analogy to very recently described borosulfates and the borophosphates, that is, tetrahedral BO4 and SeO4 units linked by common corners. In each case, the BO4 tetrahedra are surrounded by SeO4 tetrahedra.

The borosulfate story goes on--from alkali and oxonium salts to polyacids.

The structural principles of borosulfates derived from the B/S ratio are confirmed and extended to new representatives of this class showing novel motifs. According to the composition, Na[B(S2O7)2] (P2(1)/c; a=10.949(6), b=8.

Exploring a new structure family: alkali borosulfates Na5[B(SO4)4], A3[B(SO4)3] (A = K, Rb), Li[B(SO4)2], and Li[B(S2O7)2].

New alkali borosulfates were obtained by precipitation from oleum, solid-state reactions, or thermal decomposition. The crystal structures were characterized with single-crystal data. They are all based on corner-linked BO4 and SO4 tetrahedra with varying coordination of the alkali cations.

Synthesis, crystal structure and optical properties of Na2RE(PO4)(WO4) (RE = Y, Tb-Lu).

Phase-pure samples of sodium rare-earth phosphate tungstates Na(2)RE(PO(4))(WO(4)) (RE = Y, Dy-Lu) and Na(2)Y(PO(4))(WO(4)):Ln(3+) (Ln = Eu, Tb) were obtained by reaction of the respective rare-earth oxide with ammonium hydrogen phosphate with sodium tungstate Na(2)WO(4)·2H(2)O as a flux at 1220 K. According to X-ray single-crystal investigations Na(2)RE(PO(4))(WO(4)) (RE = Y, Tb-Lu) crystallise orthorhombically in space group Ibca (no. 73) (RE = Y, Z = 8, a = 1799.