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The 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Introduction: The WHO estimates that each year 5 million people are left permanently disabled after stroke. Adjuvant treatments to promote the effects of rehabilitation are urgently needed. Cortical excitability and neuroplasticity can be enhanced by non-invasive brain stimulation but evidence from sufficiently powered, randomized controlled multi-center clinical trials is absent. Methods: Neuroregeneration enhanced by transcranial direct current stimulation (tDCS) in stroke (NETS) tested efficacy and safety of anodal tDCS to the primary motor cortex of the lesioned hemisphere in the subacute phase (day 5–45) after cerebral ischemia. Stimulation was combined with standardized rehabilitative training and repeatedly applied in 10 sessions over a period of 2 weeks in a planned sample of 120 patients. Primary outcome parameter was upper-extremity function at the end of the 2-weeks intervention period of active treatment or placebo (1:1 randomization), measured by the upper-extremity Fugl-Meyer assessment. Sustainability of the treatment effect was evaluated by additional follow-up visits after 30 and 90 days. Further secondary endpoints included metrics of arm and hand function, stroke impact scale, and the depression module of the patient health questionnaire. Perspective: NETS was aimed at providing evidence for an effective and safe adjuvant treatment for patients after stroke. Trial registration: ClinicalTrials.gov Identifier NCT00909714. Registered May 28, 2009. [ABSTRACT FROM AUTHOR]

Introduction: The WHO estimates that each year 5 million people are left permanently disabled after stroke. Adjuvant treatments to promote the effects of rehabilitation are urgently needed. Cortical excitability and neuroplasticity can be enhanced by non-invasive brain stimulation but evidence from sufficiently powered, randomized controlled multi-center clinical trials is absent. Methods: Neuroregeneration enhanced by transcranial direct current stimulation (tDCS) in stroke (NETS) tested efficacy and safety of anodal tDCS to the primary motor cortex of the lesioned hemisphere in the subacute phase (day 5–45) after cerebral ischemia. Stimulation was combined with standardized rehabilitative training and repeatedly applied in 10 sessions over a period of 2 weeks in a planned sample of 120 patients. Primary outcome parameter was upper-extremity function at the end of the 2-weeks intervention period of active treatment or placebo (1:1 randomization), measured by the upper-extremity Fugl-Meyer assessment. Sustainability of the treatment effect was evaluated by additional follow-up visits after 30 and 90 days. Further secondary endpoints included metrics of arm and hand function, stroke impact scale, and the depression module of the patient health questionnaire. Perspective: NETS was aimed at providing evidence for an effective and safe adjuvant treatment for patients after stroke. Trial registration: ClinicalTrials.gov Identifier NCT00909714. Registered May 28, 2009. [ABSTRACT FROM AUTHOR]

Copyright of Nachrichten aus der Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

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 °C). Both form colorless, moisture‐sensitive crystals and exhibit layered anionic networks. [BMIm][Sn3Cl7] contains "horseshoe"‐like ∞1(SnCl1/1Cl2/2) chains that are linked via [SnCl3]− anions to ∞2[Sn3Cl7]− zigzag‐planes. [BMIm][Sn4Br9] contains a complex ∞2[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[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 %. [ABSTRACT FROM AUTHOR]

[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+. [ABSTRACT FROM AUTHOR]

[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+. [ABSTRACT FROM AUTHOR]

A better understanding of motor recovery after stroke requires large-scale, longitudinal trials applying suitable assessments. Currently, there is an abundance of upper limb assessments used to quantify recovery. How well various assessments can describe upper limb function change over 1 year remains uncertain. A uniform and feasible standard would be beneficial to increase future studies' comparability on stroke recovery. This review describes which assessments are common in large-scale, longitudinal stroke trials and how these quantify the change in upper limb function from stroke onset up to 1 year. A systematic search for well-powered stroke studies identified upper limb assessments classifying motor recovery during the initial year after a stroke. A metaregression investigated the association between assessments and motor recovery within 1 year after stroke. Scores from nine common assessments and 4,433 patients were combined and transformed into a standardized recovery score. A mixed-effects model on recovery scores over time confirmed significant differences between assessments (P < 0.001), with improvement following the weeks after stroke present when measuring recovery using the Action Research Arm Test (β = 0.013), Box and Block test (β = 0.011), Fugl–Meyer Assessment (β = 0.007), or grip force test (β = 0.023). A last-observation-carried-forward analysis also highlighted the peg test (β = 0.017) and Rivermead Assessment (β = 0.011) as additional, valuable long-term outcome measures. Recovery patterns and, thus, trial outcomes are dependent on the assessment implemented. Future research should include multiple common assessments and continue data collection for a full year after stroke to facilitate the consensus process on assessments measuring upper limb recovery. [ABSTRACT FROM AUTHOR]

Nine Ge−Fe carbonyl cluster compounds are prepared via ionic liquids‐based synthesis. This includes the novel compounds [EMIm][Fe(CO)3I(GeI3)], [EHIm][Fe(CO)3I(GeI3)], [BMIm][GeI2{Fe(CO)4}2(μ‐I)][AlCl4]2, [GeI2{Fe(CO)4}2(μ‐I)][Fe(AlBr4)3], [BMIm]2[(FeI2)0.75{Fe(CO)2I(GeI3)2}2], and [EHIm][Fe(CO)4(GeI2)2Fe(CO)3GeI3] as well as the previously reported compounds (Fe(CO)4(GeI3)2, FeI4{GeI3Fe(CO)3}2, and Ge12{Fe(CO)3}8(μ‐I)4 (EMIm: 1‐ethyl‐3‐methylimidazolium, EHIm: 1‐ethylimidazolium, BMIm: 1‐butyl‐3‐methylimidazolium). With this series of compounds, a comparison of synthesis conditions and structural features is possible and, for instance, allows correlating the composition and structure of the respective Ge−Fe carbonyl cluster compounds with the type and acidity of the ionic liquid. With [EMIm][{GeI3}2Fe(CO)3I], moreover, we can exemplarily show the thermal decomposition as a single‐source precursor in the ionic liquid, resulting in bimetallic Ge−Fe nanoparticles with small size and narrow size distribution (7.0±1.4 nm). [ABSTRACT FROM AUTHOR]

[SnI8{Fe(CO)4}4][Al2Cl7]2 contains the [SnI8{Fe(CO)4}4]2+ cation with an unprecedented highly coordinated, bicapped SnI8 prism. Given the eightfold coordination with the most voluminous stable halide, it is all the more surprising that this SnI8 arrangement is surrounded only by fragile Fe(CO)4 groups in a clip‐like fashion. Inspite of a predominantly ionic bonding situation in [SnI8{Fe(CO)4}4]2+, the I−⋅⋅⋅I− distances are considerably shortened (down to 371 pm) and significantly less than the van der Waals distance (420 pm). The title compound is characterized by single‐crystal structure analysis, spectroscopic methods (EDXS, FTIR, Raman, UV/Vis, Mössbauer), thermogravimetry, and density functional theory methods. [ABSTRACT FROM AUTHOR]

[SnI8{Fe(CO)4}4][Al2Cl7]2 enthält ein [SnI8{Fe(CO)4}4]2+‐Kation mit einem beispiellos hochkoordinierten, zweifach überdachten SnI8‐Prisma. In Anbetracht der achtfachen Koordination mit dem voluminösesten, stabilen Halogenid ist es umso erstaunlicher, dass die SnI8‐Baugruppe nur von fragilen Fe(CO)4‐Gruppen klammerartig umgeben ist. Trotz der überwiegend ionischen Bindungssituation in [SnI8{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. [ABSTRACT FROM AUTHOR]

The novel tellurium rhenium carbonyls [TeI2Re(CO)5][AlCl4] (1), [BMIm][Te2I4(μ-I)2Re(CO)4] (2), {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) and [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) were prepared by reacting TeI4 and Re2(CO)10 in ionic liquids (ILs). [TeI2Re(CO)5][AlCl4] (1) was obtained in a mixture of [BMIm]Cl (BMIm: 1-butyl-3-methylimidazolium) and AlCl3 (ratio: 1 : 1) and contains a [TeI2Re(CO)5]+ cation. Increasing the amount of AlCl3 ([BMIm]Cl : AlCl3 = 1 : 2) results in [BMIm][Te2I4(μ-I)2Re(CO)4] (2) with the anion [Te2I4(μ-I)2Re(CO)4]−. At a [BMIm]Cl to AlCl3 ratio of 1 : 3, {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) was realized with a Te3I3 ring and μ3-coordinating iodine. Finally, [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) was prepared in [BMIm][OTf] (OTf: triflate) and contains the ufosan-like anion [(Te2)3{Re(CO)3}2{Re(CO)4}3]− with three Te22− and two Re(CO)3+ units that establish a distorted heterocuban-like cage. The compounds were characterized by single-crystal structure analysis, energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), and infrared spectroscopy (FT-IR). The course of the reaction and the formation of the four novel tellurium-rhenium carbonyls can be directly correlated to the reaction conditions and especially to the acidity of the IL. [ABSTRACT FROM AUTHOR]

[Pb{Mn(CO)5}3][AlCl4] containing a trigonal planar PbMn3 cluster was obtained by the reaction of PbCl2 and Mn2(CO)10 in the ionic liquid [BMIm][AlCl4]. The title compound is composed of [Pb{Mn(CO)5}3]+ carbonyl cations and [AlCl4]− anions that are connected to infinite zig-zag chains. The [Pb{Mn(CO)5}3]+ cation exhibits a central PbMn3 cluster with three equal Pb–Mn single bonds, resulting in an almost equilateral triangle of three manganese atoms with a formal Pb+I in its center. Such a cluster and compound were identified for the first time. In addition to single-crystal structure analysis, the composition, structure and properties were further characterized by density functional theory (DFT) calculations, energy dispersive X-ray spectroscopy (EDXS), and Fourier-transform infrared spectroscopy (FT-IR), as well as optical spectroscopy (UV-Vis). [ABSTRACT FROM AUTHOR]

The germanium–iron cluster Ge12{Fe(CO)3}8(μ-I)4 was prepared by reacting GeI4 and Fe2(CO)9 in [BMIm]Cl/AlCl3 as ionic liquid (BMIm: 1-butyl-3-methylimidazolium). The cluster contains a Ge12Fe8 metal core consisting of a central Ge4 rectangle, two Ge2 pairs, and four single Ge atoms. These Ge units are interconnected by Fe atoms to a real Ge–Fe cluster. According to DFT calculations, Hund's localization criterion is fulfilled for the whole cluster if we assume three different atomic charges on the Ge4, Ge2, and Ge units. [ABSTRACT FROM AUTHOR]

Dark red and brick red transparent crystals of FeI4{GeI3Fe(CO)3}2 ( 1) and (GeI3)2Fe(CO)4 ( 2) were obtained by reacting GeI4 and Fe2(CO)9 or Fe3(CO)12 in a mixture of [BMIM]Cl and AlCl3 as ionic liquid (BMIm = 1-butyl-3-methylimidazolium). According to X-ray structure analysis based on single crystals, the title compounds exhibit cluster units with Fe-Ge bonds. FeI4{GeI3Fe(CO)3}2 consists of two GeI2I1/2-Fe(CO)3I2/2 units that are interlinked by a distorted octahedral FeI6/2 group. (GeI3)2Fe(CO)4 consists of two GeI3 units that are connected by a square planar Fe(CO)4 group with a linear Ge-Fe-Ge unit. Depending on the synthesis conditions, interestingly, (GeI3)2Fe(CO)4 crystallizes either in P21/ n ( 2a) or in P 1 ( 2b). 2a exhibits a more dense packing, whereas 2b exhibits shorter intermolecular I-I distances. Both title compounds are temperature labile and highly sensitive to oxygen, moisture and illumination, including X-ray irradiation. They decompose with release of CO in absence of certain CO atmosphere. In addition to crystal structure analysis the compounds were characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and infrared spectroscopy (FT-IR). [ABSTRACT FROM AUTHOR]

Microemulsions (MEs) are ideal for obtaining high-quality inorganic nanoparticles. As thermodynamically stable systems with a nanometer-sized droplet phase that serves as a nanoreactor, MEs have obvious advantages for the synthesis of nanoparticles. MEs also have disadvantages, such as their complexity as multicomponent systems, the low amount of obtainable nanoparticles, their limited thermal stability, the fact that hydrolyzable or oxidizable compounds are often excluded from synthesis, the partly elaborate separation of nanoparticles, as well as the removal of surface-adhered surfactants subsequent to synthesis. This Review presents some strategies to further expand the options of ME-based synthesis of inorganic nanoparticles. This comprises the crystallization of nanoparticles in 'high-temperature MEs', the synthesis of hollow nanospheres, the use of hydrogen peroxide or liquid ammonia as the polar droplet phase, and the synthesis of base metals and nitrides in MEs. [ABSTRACT FROM AUTHOR]

Mikroemulsionen (ME) sind ideal, um hochwertige anorganische Nanopartikel zu erhalten. Als thermodynamisch stabile Systeme mit einer Phase aus Nanometer‐großen Tröpfchen, die als Nanoreaktoren dienen, bieten sie für die Nanopartikelsynthese eine Reihe an Vorteilen. ME haben aber auch Nachteile, z. B. ihre Komplexität als Mehrkomponentensysteme, die geringe erhältliche Nanopartikelmenge, die begrenzte thermische Stabilität, der häufige Ausschluss hydrolysierbarer oder oxidierbarer Verbindungen von der Synthese, die partiell sehr aufwendige Abtrennung der Nanopartikel sowie die Entfernung Oberflächen‐gebundener Tenside nach der Synthese. Dieser Aufsatz soll einige Strategien zur Erweiterung der ME‐basierten Synthese anorganischer Nanopartikel aufzeigen. Dazu zählen die Kristallisation von Nanopartikeln mittels “Hochtemperatur‐ME”, die Synthese nanoskaliger Hohlkugeln, die Verwendung von H2O2 oder flüssigem NH3 als polare Tröpfchenphasen sowie die Synthese von unedlen Metallen und Nitriden in ME. Nanoreaktoren in Mikroemulsionen sind ideal, um hochwertige anorganische Nanopartikel wie Bimetalle, nanoskalige Hohlkugeln, unedle Metalle, Peroxide oder Metallnitride zu synthetisieren. Dieser Aufsatz beschreibt verschiedene Möglichkeiten jenseits der üblichen Mikroemulsionssynthese von Nanopartikeln. [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]

Functionalized 4,4′-biphenyldicarboxylic acid molecules with additional amine, alkyne, azide or nitro groups were prepared and applied in the synthesis of novel metal–organic frameworks and mixed-linker metal–organic frameworks isoreticular to DUT-5. The properties of the frameworks could be tuned by varying the number of functional groups in the materials and the amine groups were employed in post-synthetic modification reactions without changing the framework structure or significantly decreasing the porosity of the materials. [ABSTRACT FROM AUTHOR]

AgSCN nanoparticles were prepared via a water-in-oil microemulsion approach, using KSCN and AgNO3 as starting materials. The as-prepared AgSCN nanoparticles are readily crystalline, exhibit a uniform spherical shape, and have a mean diameter of 25 nm. Scanning electron microscopy (SEM) and dynamic light scattering (DLS) confirm particle size and size distribution. X-ray powder diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) prove the phase composition and purity. The particle size can be varied in a range of 25 and 40 nm (according to electron microscopy) by variation of the concentration of AgNO3 (i.e., 2 mL of 0.1 to 0.5 M AgNO3 solution). Optical spectroscopy (UV/Vis) indicates an optical band-gap of 3.78 eV without a size-depending shift at this specific particle size. The microemulsion approach can be extended to obtain further nanoscaled thiocyanates like CuSCN, AuSCN, Hg(SCN)2, and Pb(SCN)2. [ABSTRACT FROM AUTHOR]

[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central is a cubelike (Pb6I8) unit containing a nonfilled Pb6 octahedron. Each Pb of this (Pb6I8) unit is terminated on its outside by Mn(CO)5, exhibiting Pb--Mn metal-to-metal bonding (280 pm). Structurally, the (Pb6I8) unit is similar to the well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X = Cl, Br, I). In contrast to most similar cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according to Niggli notation) or the carbonyl cluster [Sn6{Cr(CO5)6}]2-, however, the nonfilled central Pb6 octahedron in [{PbMn(CO)5)}6I8]2- does not exhibit any metal-to-metal bonding. Structure and bonding of the title compound are validated by single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Based on the isolobal principle, electronegativity considerations, bond lengths, and DFT calculations including Mulliken population analysis and natural population analysis (NPA), in sum, the charge distribution of Pb is best reflected by an oxidation state of +1. [ABSTRACT FROM AUTHOR]

The bimetallic metal–organic framework Cu–Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu2+ by Ru3+ centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy. [ABSTRACT FROM AUTHOR]

A novel modification of potassium nitrate is obtained subsequent to solvothermal reaction and crystallization at reduced temperature from diethylformamid (DEF) as solvent. δ-KNO3 crystallizes with the monoclinic space group P21/ c. Most intriguing is the coordination number of potassium and oxygen as expressed by the Niggli notation δ-K8/8[NO4/4O4/2] that differs from the known modifications of potassium nitrate (α-K9/9[NO9/3], β-K9/9[NO9/3], γ-K9/9[NO9/3]). Moreover, the stacking of the NO3- anions differentiates from the known KNO3 modifications. As only few crystals were obtained, the new modification is characterized by single-crystal structure analysis as well as by Fourier-transformed infrared spectroscopy. The latter reliably points to the presence of nitrate and shows a ν(N-O) vibration centered at 1384 cm-1, but with significantly different shape and band width as compared to α-K9/9[NO9/3] as a reference. [ABSTRACT FROM AUTHOR]

By reacting Mn2(CO)10 and TeI4 in the ionic liquid[BMIm][OTf] (1-butyl-3-methylimidazolium trifluromethanesulfonate), brick-red crystals of [BMIm][(Te2)3{Mn(CO)3}2{Mn(CO)4}3]are obtained. The title compound contains the carbonyl anion[(Te2)3{Mn(CO)3}2{Mn(CO)4}3]-. Herein, three formal Te22- units and two formal Mn(CO)3+ fragments establish a distorted heterocubane-like Te6Mn2 structure. Three edges of this heterocubane are furthermore capped by Mn(CO)4+ fragments. The resulting Te6Mn5 building unit, moreover, looks very similar to the P113- anion - the so-called ufosane. The mean distances Te-Te and Te-Mn are observed with 277.6 and 264.7 pm, respectively. In addition to single-crystal structure analysis, the title compound is characterized by infrared spectroscopy (FT-IR), thermogravimetry (TG) and energy-dispersive X-ray (EDX) analysis. [ABSTRACT FROM AUTHOR]

Copyright of Nachrichten aus der Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Correction for ‘Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]’ by David Hausmann et al., Dalton Trans., 2016, 45, 16526–16532. [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]

Correction for ‘Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]’ by David Hausmann et al., Dalton Trans., 2016, 45, 16526–16532. [ABSTRACT FROM AUTHOR]

Abstract: Monodisperse, indium doped zinc oxide (IZO) nanoparticles were prepared via the polyol-mediated synthesis and incorporated into regular and inverted poly-(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl C61-butyric acid methyl ester organic photovoltaic devices as buffer layers between the active layer and the cathode. Efficient hole blocking at the particle buffer layers leads to an enhanced open-circuit voltage of the solar cells. This effect is even more pronounced for inverted device architectures. Device degradation studies revealed a solar cell performance reduction upon sample exposition to ambient atmosphere. However, this degradation is fully reversible under UV illumination. In addition, the n-doped IZO particles form suitable charge carrier transport layers for an efficient recombination in an intermediate recombination zone in tandem solar cells. Accordingly we have fabricated fully solution-processed tandem solar cells and investigated their optoelectronic properties. [ABSTRACT FROM AUTHOR]

The carbonyl cluster compound [GeRu 6 (CO) 18 HI] is unique in regard to its structure and bonding with a GeRu 6 cluster core, a planar GeRu 4 HI 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 Ru 4 (Ru 2 ) 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., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)