Crown-ether-coordination compounds of praseodymium(III), manganese(II) and the crown ether 18-crown-6 ((C2H4O)6, 18c6) are prepared in [Bu3MeN][NTf2] ([Bu3MeN]+/[(C4H9)3(CH3)N]+: tributylmethylammonium; [NTf2]-/[(CF3SO2)2N]-: bis(trifluoromethylsulfonyl)amide) as an ionic liquid. Specifically, the reaction of PrCl3, PrI3, MnCl2 or MnI2 with 18c6 at 80-100 °C results in the novel compounds [PrCl3(18c6)] (1), [MnCl2(18c6)] (2), [Bu3MeN][PrI2(18c6)][MnI4] (3), [Bu3MeN]2[MnI4] (4), [Bu3MeN]2[(Pr(I0.82Cl0.18)Cl(18c6))2][MnI4]2 (5) and [(PrCl2(18c6)MnI3)2] (6). They contain mononuclear arrangements of Pr3+ (1) and Mn2+ (2) with 18c6. 3 and 5 contain both Pr3+ and Mn2+ in a single compound but in different molecular building units ([PrI2(18c6)]+, [(Pr(I0.82Cl0.18)Cl(18c6))2]+, and [MnI4]2-) with a great distance between them (Pr-Mn > 700 pm). Finally, 6 represents the first crown-ether coordination compound with Pr3+ and Mn2+ in a single tetranuclear molecule. All title compounds are characterized by X-ray diffraction (single crystals, powder diffraction with Rietveld analysis), infrared spectroscopy, thermal analysis, and photoluminescence spectroscopy. 2-5, even when containing Pr3+ (3 and 5), show typical luminescence of Mn2+, whereas 1 and 6 show Pr3+-type transitions, with 6 showing particularly intense emission. Pr3+ → Mn2+ energy transfer is not observed, which can be ascribed to the specific distances between the luminescent centers (3 and 5) or the symmetry of the molecule (6).

We recently highlighted the value of silylated SF5 alkynes to access a variety of fundamental SF5 containing building blocks. Herein, we report a solution to the previously reported synthetic bottleneck as well as identified (E)-(1-chloro-2-pentafluoro-6-sulfaneyl)-vinyl)triethylsilane as a second generation platform chemical. This versatile platform reagent is thermally stable, easy to handle, shows high shelf-stability, can be accessed on multi-gram scale and grants facile benchtop access to a variety of fundamental known and unknown SF5-containing building blocks under very mild conditions. In this work we investigated its nucleophilic substitution by S- and N-nucleophiles. The reagent can be activated selectively allowing access to (E)-configured enamines (up to >99% yield), the first synthetically useful access to (E)-configured -vinyl sulfides (up to 99%) and S,S-acetals (up to 97%) in a single reaction step. Further processing allowed convertion into S,S-ketene acetals (up to 90%), which can be hydrolyzed to yield the corresponding esters (up to 88%) as well as -SF5 acetic acid (>99%). Furthermore, we addressed the previous accessibility restrictions on triisopropyl silyl acetylene sulfur pentafluoride (TASP) the development of a novel in-situ elimination strategy and identified the TBDMS derivative of TASP as an accessible, stable and reactive reagent to prepare the complementary (Z)-configured -vinyl sulfides (up to 71%) in a single reaction step.

AbstractThe carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi‐center bonding, and an aromatic ring current similar to benzene (9‐10 nA T−1). The open‐shell cluster core is a Ge‐centered five‐membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly‐coordinating ionic liquid.

The cover picture presents a structural motif of a distorted Pd2Cl2 square in solid PdCl(NO). This iconic compound was firstly synthesized during outstanding research in the late 1950s in Munich, which led to the development of the Wacker process for the conversion of ethene into acetaldehyde by catalysis with PdCl2. More than sixty years after its synthesis, crystals of PdCl(NO) were prepared for the first time and the structure determined by X-ray diffraction. In the monoclinic structure distorted Pd4Cl4 octagons in chair arrangement are interconnected to corrugated layers, forming a two-dimensional polymer insoluble in common solvents. In this compound each Pd atom is connected to a N-O group, bonded alternatively up and down with a Pd-N-O angle of 129°. The bonding situation in PdCl(NO) was investigated by vibrational, electronic and X-ray absorption (XAS) spectroscopies. The XAS measurement at the KIT synchrotron facility uncovers that the charge located at the Pd atom in PdCl(NO) is comparable to that in PdCl2 or PdO (DOI: 10.1002/zaac.202200337).

Abstract The novel tin bromido aluminates [Sn3(AlBr4)6](Al2Br6) (1), Sn(AlBr4)2 (2), [EMIm][Sn(AlBr4)3] (3) and [BMPyr][Sn(AlBr4)3] (4) ([EMIm]: 1‐ethyl‐3‐methylimidazolium, [BMPyr]: 1‐butyl‐1‐methyl‐pyrrolidinium), are obtained from a ionic‐liquid‐based reaction of AlBr3 and SnCl2 or SnBr2, resulting in colorless and transparent crystals. 1 contains a neutral, inorganic ∞3[Sn3(AlBr4)6] network filled with intercalated Al2Br6 molecules. 2 represents a 3D structure isotypic to Pb(AlCl4)2 or α‐Sr[GaCl4]2. 3 and 4 exhibit infinite ∞1[Sn(AlBr4)3]n− chains that are separated by the voluminous [EMIm]+/[BMPyr]+ cations. All title compounds contain Sn2+ coordinated by AlBr4 tetrahedra, resulting in chains or 3D networks. Moreover, all title compounds show photoluminescence due to Br−→Al3+ ligand‐to‐metal charge‐transfer excitation, followed by 5s2p0←5s1p1 emission on Sn2+. Most surprisingly, the luminescence is highly efficient (quantum yield >50 %). Specifically, 3 and 4 exhibit outstanding quantum yields of 98 and 99 %, which are the highest values observed for Sn2+‐based luminescence so far. The title compounds have been characterized by single‐crystal structure analysis, elemental analysis, energy‐dispersive X‐ray analysis, thermogravimetry, infrared and Raman spectroscopy, UV‐Vis and photoluminescence spectroscopy.

The pseudo-ternary tin(II) halide [BMPyr]2[SnCl4] can be obtained just by mixing the starting materials [BMPyr]Cl and SnCl2 at room temperature without additional solvents. The compound shows bright Sn(II)-based emission of deep-red light (λmax: 740 nm) with a quantum yield of 88 ± 3% after optimised synthesis. Characterization is performed by X-ray structure analysis, infrared and fluorescence spectroscopy. Exemplary fluorescent thinfilms are realized by solvent processing.

During outstanding research in the late 1950s in Munich, which led to the development of the Wacker process for converting ethene into acetaldehyde by catalysis of PdCl2, black insoluble nitrosyl-palladium chloride (PdCl(NO)) was obtained. More than sixty years after its first synthesis, its crystal structure was now determined by X-ray diffraction. PdCl(NO) (mP16, P2(1)/c, a=10.2684(5), b=4.0737(2), c=7.8456(4) angstrom, beta=111.125(1)degrees, wR2=0.0572) consists of distorted Pd4Cl4 octagons in chair arrangement to which four distorted Pd2Cl2 squares are annulated on every second edge. In this arrangement each of the two Pd atoms of the squares are connected to one N-O group, bonded alternatively up and down to the Pd atoms with a Pd-N-O angle of 129 degrees. Such a square has the composition of the dimer which was found in the mass spectrum at 343.6 m/e. The octagons with four squares are interconnected to corrugated layers in the b-c-plane as a two-dimensional polymer.

The novel tin(II) oxychloride [BMIm][Sn5O2Cl7] (BMIm = 1-butyl-3-methylimidazolium) is obtained by the room-temperature reaction (25 °C) of black SnO and SnCl2 in [BMIm]Cl/SnCl2 as an ionic liquid. The title compound can be described as composed of noncharged, infinite ∞1(Sn2OCl2) strands that are embedded in a saline matrix of [BMIm]+ and [SnCl3]-. The ∞1(Sn2OCl2) strands consist of a backbone of edge-sharing OSn4/2 tetrahedra, which represent one-dimensional (1D) strands cut out of the layer-type structure of SnO. In [BMIm][Sn5O2Cl7], the ∞1(Sn2OCl2) strands, which mimic a 1D semiconductor, are terminated by chlorine atoms, whereas they are interconnected by oxygen atoms in the 2D semiconductor SnO. The view of the noncharged ∞1(Sn2OCl2) strands in a saline [BMIm][SnCl3] matrix is validated by dissolution experiments. Thus, electron microscopy and Raman spectroscopy show a deconstruction of [BMIm][Sn5O2Cl7] single crystals after treatment with chloroform with a dissolution of [BMIm][SnCl3], the formation of SnCl2 needles, and tin oxide as a solid remain.

AbstractÜber weiße Magnete, ungewöhnliche Hydride, ein Elektrid gewonnen aus Plasma, den Kampf zwischen Lewis und Brønsted, Synthesen unter hohem und höherem Druck, nachhaltige Batteriematerialien sowie Katalysatoren für die Wasserspaltung und mehr.

The halogenido stannates(II) [BMIm][Sn3Cl7] and [BMIm][Sn4Br9] are obtained by ionic-liquid-based synthesis with SnX2 and [BMIm]X (X=Cl, Br; [BMIm]=1-butyl-3-methylimidazolium) near room temperature (45-50 degrees C). Both form colorless, moisture-sensitive crystals and exhibit layered anionic networks. [BMIm][Sn3Cl7] contains "horseshoe"-like (1)(infinity)(SnCl1/1Cl2/2) chains that are linked via [SnCl3](-) anions to (2)(infinity)[Sn3Cl7](-) zigzag-planes. [BMIm][Sn4Br9] contains a complex (2)(infinity)[Sn4Br9](-) network with altogether four different crystallographic Sn2+ sites and different coordination. For comparison with these complex halogenido stannates(II), PbCl2/PbBr2 are reacted with similar conditions, which, however, only results in [BMIm][PbCl3] containing (1)(infinity)[PbCl3](-) chains. Beside the crystal structures, the thermal and optical properties are examined and feature certain emission of visible light for all title compounds at room temperature. Whereas the quantum yields of [BMIm][Sn4Br9] (3 %) and [BMIm][PbCl3] (21 %) are low, [BMIm][Sn3Cl7] shows surprisingly efficient photoluminescence with a quantum yield of 46 %.

An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

[BMIm][Sn(AlCl4)3] (1) ([BMIm]: 1-butyl-3-methylimidazolium), [BMPyr][Sn(AlCl4)3] (2) ([BMPyr]: 1-butyl-1-methyl-pyrrolidinium), and [BMIm][Pb(AlCl4)3] (3) are obtained by reaction of SnCl2/PbCl2 in [BMIm]Cl/[BMPyr]Cl/AlCl3-based ionic liquids. The colourless crystals of the title compounds contain infinite 1∞[M(AlCl4)3]n- chains (M: Sn, Pb) that are separated by the voluminous [BMIm]+/[BMPyr]+ cations. The central Sn2+/Pb2+ is coordinated by chlorine in the form of distorted squared anti-prismatic polyhedra. Each Cl atom, in turn, is part of an [AlCl4]- tetrahedron that interlinks Sn2+/Pb2+ to the chain-like building unit. In addition to the novel structural arrangement, all title compounds surprisingly show intense white-light emission. Although Sn2+ and Pb2+ are well-known as dopants in conventional phosphors, efficient luminescence via s-p-transitions of compounds containing Sn2+/Pb2+ in molar quantities and as regular lattice constituents is rare. The emission of [BMIm][Sn(AlCl4)3] and [BMPyr][Sn(AlCl4)3] is very efficient with quantum yields of 51 and 76%, which belong to the highest values known for s-p-based luminescence of Sn2+.

The crown-ether coordination compounds ZnX2(18-crown-6), EuX2(18-crown-6) (X: Cl, Br, I), MnI2(18-crown-6), Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) are obtained by ionic-liquid-based synthesis. Whereas MX2(18-crown-6) (M: Zn, Eu) show conventional structural motives, Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) exhibit unusual single MnX4 tetrahedra coordinated to the crown-ether complex. Surprisingly, some compounds show outstanding photoluminescence. Thus, rare Zn2+-based luminescence is observed and unexpectedly efficient for ZnI2(18-crown-6) with a quantum yield of 54%. Unprecedented quantum yields are also observed for Mn3I6(18-crown-6)2, EuBr2(18-crown-6), and EuI2(18-crown-6) with values of 98, 72, and 82%, respectively, which can be rationalized based on the specific structural features. Most remarkable, however, is Mn2I4(18-crown-6). Its specific structural features with finite sensitizer-activator couples result in an extremely strong emission with an outstanding quantum yield of 100%. Consistent with its structural features, moreover, anisotropic angle-dependent emission under polarized light and nonlinear optical (NLO) effects occur, including second-harmonic generation (SHG). The title compounds and their optical properties are characterized by single-crystal structure analysis, X-ray powder diffraction, chemical analysis, density functional theory (DFT) calculations, and advanced spectroscopic methods.

GaSeCl5O is a new inorganic molecular compound prepared from SeO2, SeCl4, and GaCl3 at 50 °C in quantitative yield. The structure of the title compound is described by GaCl3(OSeCl2) molecules with a tetrahedrally coordinated Ga atom and a pseudo-tetrahedrally coordinated Se atom (including lone pair of Se(IV)) that are bridged by oxygen. GaSeCl5O crystallizes in the polar chiral space group P61, which is rarely observed for molecular structures. The compound is characterized by X-ray structure analysis based on single crystals and powder samples, thermogravimetry, infrared and Raman spectroscopy as well as by second harmonic generation (SHG) measurements. The experimental data are complemented by density functional theory calculations. GaSeCl5O shows one of the strongest SHG signals known in the visible part of the electromagnetic spectrum (480-700 nm) with an SHG intensity 10 times higher than potassium dihydrogen phosphate (KDP). This is in accordance with the phase matchability and a strong dipole moment (|μ| = 8.3 D for a molecule in the crystal lattice). Such a strong SHG effect is also remarkable since GaSeCl5O-unlike most of the materials with strong SHG intensity-is an inorganic molecular compound.

[SnI 8 {Fe(CO) 4 } 4 ][Al 2 Cl 7 ] 2 enthält ein [SnI 8 {Fe(CO) 4 } 4 ] 2+ ‐Kation mit einem beispiellos hochkoordinierten, zweifach überdachten SnI 8 ‐Prisma. In Anbetracht der achtfachen Koordination mit dem voluminösesten, stabilen Halogenid ist es umso erstaunlicher, dass die SnI 8 ‐Baugruppe nur von fragilen Fe(CO) 4 ‐Gruppen klammerartig umgeben ist. Trotz der überwiegend ionischen Bindungssituation in [SnI 8 {Fe(CO) 4 } 4 ] 2+ sind die I − ⋅⋅⋅I − ‐Abstände verkleinert (bis zu 371 pm) und liegen deutlich unter dem Van‐der‐Waals‐Abstand (420 pm). Charakterisiert wurde die Titelverbindung durch Einkristallstrukturanalyse, spektroskopische Methoden (EDXS, FT‐IR, Raman, UV/Vis, Mößbauer), Thermogravimetrie und Dichtefunktionaltheorie.