ALBERT

Description: The reaction of the nitrosyl carbonyl complexes [Fe(NO) 2 (CO) 2 ] and [Co(NO)(CO) 3 ] with the decacarbonyldimetalates [ M 2 (CO) 10 ] 2– ( M = Cr and Mo) in THF as the solvent at room temperature was investigated. Thereby a substitution of one nitrosyl ligand towards carbon monoxide was observed in each case. Both reactions afforded the known metalate complexes [Fe(NO)(CO) 3 ] – and [Co(CO) 4 ] – , respectively. These species were isolated as their corresponding PPN salts [PPN + = bis(triphenylphosphane)iminium cation] in nearly quantitative yields. The products were unambiguously identified by their IR spectroscopic and elemental analytic data as well as by their characteristic colors and melting points.

Description: The formation and structural aspects of some metal complexes of thiosalicylic acid (TSA) were studied. The μ-bridging tetra-coordinated Ru complex, [Ru(C 6 H 4 (CO 2 )(μ-S)(H 2 O)] 2 ( 1 ) was formed by hydrothermal reaction of TSA with RuCl 3 . The complexes [ M (dtdb)(phen)(H 2 O)] n ( 2 – 4 ) ( M = Zn II , Co II , Ni II , dtdb = 2,2′-dithiodibenzoate anion, phen = 1,10-phenanthroline) were obtained by the slow diffusion technique and the in situ S–S bond formation was confirmed by elemental, spectral and X-ray analysis. Reaction of TSA with CuCl 2 and 2,2′-bipyridine (bipy) under the slow diffusion technique yielded the dimer [Cu(tdb)(bipy)] ( 5 ) (tdb = thiodibenzoic acid), where the in situ generation of 2,2′-thiodibenzoic acid was observed.

Description: Zinc and cadmium diphenate (dip, biphenyl-2,2′-dicarboxylate) coordination polymers containing conformationally flexible dipyridylamide ligands show diverse chain and layer topologies as determined by single-crystal X-ray diffraction. [Cd(dipH) 2 (bdin)] n ( 1 ) [bdin = N , N ′-(butane-1,3-diyl)diisonicotinamide] shows a simple 1D zigzag chain structure. {[Cd(dip)(pdin)(H 2 O)] · 1.25H 2 O} n ( 2 ) [pdin = N , N ′-(propane-1,3-diyl)diisonicotinamide] shows bilayer slabs formed by interleaving of (4,4) rectangular grid layers. {[Zn 2 (dip) 2 (3-pna) 2 ] · 3H 2 O} n ( 3 ) (3-pna = 3-pyridylnicotinamide) manifests a rare 4-connected 1D ribbon topology. {[Cd(dip)(4-ppbp)] · 2H 2 O} n ( 4 ) [4-ppbp = propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone)] shows a 3,5-connected layer with (4 2 6)(4 2 6 7 8) 3,5L2 topology. {[Zn 4 (dip) 4 (H 2 O) 2 (4-ppbp) 2 ] · 12H 2 O} n ( 5 ) exhibits 2D 3,6-connected layers with (4 3 ) 2 (4 6 6 6 8 3 ) kgd topology featuring embedded R(8)A(2) classification 10-membered water clusters. Compounds 1 , 4 , and 5 undergo violet or blue-violet fluorescence upon ultraviolet irradiation. Thermal decomposition behavior of the new phases is also discussed.

Description: A series of higher sodium hydrogen fluorides were synthesized and structurally characterized. Sodium tetrahydrogen pentafluoride, NaH 4 F 5 , crystallizes in space group type I 4 1 / a with cell parameters a = 6.0275(4), c = 11.6208(13) Å, V = 422.19(7) Å 3 , Z = 4 at 100 K. Sodium trihydrogen tetrafluoride, NaH 3 F 4 , crystallizes in space group type R 3 with cell parameters a = 6.5139(4), c = 13.4040(15) Å, V = 492.55(8) Å 3 , Z = 6 at 100 K. Sodium dihydrogen trifluoride, NaH 2 F 3 , crystallizes in space group type Pnma with cell parameters a = 7.9276(9), b = 3.4514(3), c = 9.6937(10) Å, V = 265.23(5) Å 3 , Z = 4 at 100 K. The investigations were complemented by IR spectroscopy and theoretical calculations. NaH 2 F 3 was additionally characterized by means of powder neutron diffraction. All observed F–H ··· F hydrogen bonds are unsymmetric, close to linearity and can be considered as strong hydrogen bonds.

Description: The cover picture shows the crystal structure of α-LiAlH 4 in space group type P 2 1 / c view along 00 1 ). Lithium atoms (green) and aluminium atoms (purple) are surrounded by five and four hydride anions (white), respectively. The coordination of hydride anions by metal cations represents the simplest numerical solution ( Σ tot = Σ num ) according to Beck's crystal chemical indices of ion segregation Σ and electrostatic imbalance Y . The background shows the crystal structure of EuMg 2 H 6 which in contrast does not conform to the simplest numerical solution. More details are discussed in the article Voss and Kohlmann on pp. 1037 ff .

Description: By reaction of pentacarbonyltetrafluoroboratorhenium with the neutral methylated xanthine derivatives the cationic complexes [(OC) 5 Re-L] + BF 4 – (L = caffeine, isocaffeine, theophylline, theobromine) were prepared and spectroscopically characterized.

Description: Structural, electronic, and vibrational spectroscopic investigations were performed for the solid solution NaP 7– x As x up to x = 3.5 featuring a helical polypnictide substructure. Depending on the As content the LiP 7 (for x = 0 to 0.8 and 2.5 to 3.5) or KP 15 ( x = 1.0 to 2.4) structure type is realized up to an maximum As content of x = 3.5. The crystal structures of two selected phases were determined and the distribution of As in the polyanionic substructure was determined. The full solid solution up to x = 7 was subject to a quantum chemical DFT analysis in order to get insights into the stabilities and phase formation tendencies. Van der Waals interactions between the structure subunits were estimated and first principle investigations towards a delamination and nano structuring of NaP 7– x As x crystals into one-dimensional semiconductors were performed.

Description: Dilithium and magnesium alkanediides of the types Li(CH 2 ) n Li and [Mg(CH 2 ) n ] x represent substance classes with a long tradition, however, the interest in these compounds ceased in recent years. Numerous reasons account for the vanishing attention such as challenging synthetic procedures, poor to moderate yields, complex structures in solution and the solid state, and complex equilibria in solution. Degradation processes (ether degradation, β-hydride elimination, indirect reduction reactions) increase the intricacy of these compounds because these degradation products take part in the solution equilibria. Thus, chloride and hydride ions are able to act as templates for lithium cages yielding e.g. [(Et 2 O) 4 Li] + [Li 12 (C 4 H 8 ) 6 (@- X )] – ( X = H, Cl) with an X -centered Li 12 icosahedron. Despite these challenges, the dilithium and magnesium alkanediides are a fascinating substance class with a rich chemistry by its own (such as Schlenk-type equilibria) and as metalating and reducing reagents. The enormous sensitivity toward moisture (hydrolysis reactions) and air (oxidation processes) and reactivity toward ethereal media (ether degradation reactions) also interferes with the dianionic alkanes because alkoxide and oxide ions are strong Lewis bases and as such, are easily integrated in the structures as bridging anions or centers of metal cages. Thus, aerial oxidation leads to insertion of an oxygen atom into the metal–carbon bond yielding 1-oxaalkanediides. Alternatively, magnesium 1-oxaalkanediides can be prepared by a two-step protocol from chloroalkanol, starting with deprotonation of the alcohol functionality with a Grignard reagent and a subsequent reduction of the C–Cl unit with magnesium turnings. This protocol leads to compounds of the type [{MgO(CH 2 ) n } x (MgCl 2 ) y ] with additional ether bases saturating the coordination spheres of the magnesium atoms. All these reactions (increasing degradation processes and reactions with inadvertently introduced traces of oxygen and moisture) limit the durability of such solutions, subsumed as aging of these dilithium and magnesium dialkanediide stock solutions, which lead to a changing (decreasing) reactivity of such reagents.

Description: The Front Cover shows the Turquoise-crested Mot Mot bird, native to Trinidad, whose tail paddles resemble the pyridyl rings in the N,N-(butane-1,3-diyl)diisonicotinamide (bdin) ligands in a 1D cadmium coordination polymer containing the diphenate ligand, which is held in the bird's beak. Other 1D and 2D zinc and cadmium diphenate coordination polymers with different dipyridylamide ligands are discussed in the article. The total solar eclipse that occurred in the USA on August 21, 2017 is also commemorated in the cover art. More details are discussed in the article by Martinez and LaDuca on pp. 1118 ff .

Description: Solid state metathesis reactions of PbCl 2 with metal carbodiimides yielded multinary lead carbodiimide chlorides A Pb 2 Cl 3 (CN 2 ) ( A = Li, Na, Ag). Their crystal structures strongly relate to the mineral Bideauxite [AgPb 2 Cl 3 (OH,F) 2 ], all crystallizing in the space group Fd 3 m . The same crystal structure exists not only with chloride but also with bromide. Another compound obtained in this system is LiPbCl(CN 2 ) with a crystal structure that can be considered as the result of an intercalation of LiCl into the layered structure of Pb(CN 2 ).

Description: The first filled Bi 9 5+ polycation was isolated in the form of [RhBi 9 ](AlCl 4 ) 4 crystals by dissolution of the solid precursor Bi 12– x Rh X 13– x in the Lewis-acidic ionic liquid [BMIm]Cl·3.6AlCl 3 (BMIm = 1-butyl-3-methylimidazolium) at 140 °C. In the monoclinic crystal structure [ P 2 1 / n, a = 1217.5(2) pm, b = 1741.6(3) pm, c = 5085.7(7) pm, β = 90.117(8)°], the almost spherical [RhBi 9 ] 4+ polycations (approximate D 3 h symmetry; Rh–Bi 276 ± 3 pm) show pronounced orientational disorder. Shiny black needles of Bi 7 RhI 8 were obtained from the reaction of rhodium, bismuth, and BiI 3 in the ionic liquid [BMIm]Cl · 1.3AlCl 3 at 200 °C. Bi 7 RhI 8 [ P 2 1 / n, a = 943.10(1) pm, b = 1582.40(1) pm, c = 1645.40(1) pm, β = 95.48(1)°] is isostructural to Bi 7 RhBr 8 and consists of molecular clusters [(RhBi 7 )I 8 ]. The rhodium atom centers a pentagonal bipyramid of bismuth atoms, and the two apical bismuth atoms are in square-planar coordination of iodide ions. DFT-based calculations indicate strong bismuth-rhodium bonding with predominantly covalent character for both clusters. The electronic structure of the Bi 9 5+ cage is notably modified by this interaction, but the characteristic bonding features of the host cluster with the D 3 h configuration are still maintained. In Bi 7 RhI 8 , on the other hand, bonding is dictated by the spatial distribution of mutually repelling iodine atoms, and the Bi–Rh bonding is highly polar.

Description: The Schiff N -allylamine-4-(ethylenediamine-5-methylsalicylidene)-1,8-naphthalimide (H 2 L) and its copper(II) complex, [Cu(HL) 2 ] · 0.5DMF, were synthesized and characterized. The crystal structure of the Cu II complex reveals a slightly distorted square-planar arrangement provided by two N and O donors from two deprotonated ligands. In addition, the DNA-binding properties of the ligand and Cu II complex were investigated by fluorescence spectra, electronic absorption, and viscosity measurements. The experimental studies of the DNA-binding properties indicated that the ligand and Cu II complex reacted with DNA via intercalation binding mode, and binding affinity for DNA takes the order: ligand 〉 Cu II complex. The antioxidant assay in vitro suggested that both exhibited potential intensely antioxidant properties, and the ligand is more effective than its Cu II complex.

Description: The reactions of the monomeric phosphanylboranes Ph 2 P–BH 2 · NMe 3 ( 1a ) and t BuHP–BH 2 · NMe 3 ( 1b ) with the main group Lewis acids BH 3 and BBr 3 yield the adducts H 3 B · Ph 2 P–BH 2 · NMe 3 ( 2a ) and H 3 B · t BuHP–BH 2 · NMe 3 ( 2b ), Br 3 B · Ph 2 P–BH 2 · NMe 3 ( 3a ), and Br 3 B · t BuHP–BH 2 · NMe 3 ( 3b ). All these compounds were completely characterized by single-crystal X-ray structure analysis, NMR and IR spectroscopy as well as mass spectrometry and DFT computations. The secondary and tertiary phosphines 1a and 1b behave as classical Lewis bases to coordinate B X 3 ( X = H, Br) as terminal groups.

Description: The linkage isomerization of [Pt(SCN) 2 (bipy)] complex in solid-state was investigated by differential scanning calorimetry (DSC) at diverse heating rates. The conversion of the bis-thiocyanato isomer (–SCN) 2 to the bis-isothiocyanato isomer (–NCS) 2 was accompanied by the appearance of an exothermic peak. However, no DSC peak was obtained for isomerization of the (–NCS) 2 . The results imply that the (–SCN) 2 isomer is metastable which can convert to the stable isomer (–NCS) 2 at elevated temperatures. Assuming a two-stage irreversible isomerization, the enthalpy changes of the first stage Δ H SCN 1 and also second stage Δ H SCN 2 isomerization were obtained (–2.99 ± 0.44 and –2.81 ± 0.45 kJ · mol –1 , respectively) using the mathematical resolution of the observed DSC peaks. The thermokinetic parameters of this conversion were determined using Kissinger method. The activation energy values for the first and second stages of isomerization are evaluated, 101.78 ± 7.58 and 106.26 ± 5.87 kJ · mol –1 , respectively. The low values of the activation enthalpy, Δ H ‡ and the high negative activation entropy Δ S ‡ , obtained by Eyring equation, supported an associative mechanism. A DFT study was employed to detect the electronic structures and the thermodynamic stabilities of the three linkage isomers and the transition states.

Description: The new compound [Ni(2amp) 3 ] 2 [Sn 2 S 6 ] · 9.5H 2 O ( 1 ) was obtained at room temperature using Na 4 SnS 4 · 14H 2 O and [Ni(2amp) 3 ][ClO 4 ] 2 [2amp = 2-(aminomethyl)pyridine] or [Ni(en) 3 ]Cl 2 · 2H 2 O as starting materials. The synthesis is fast and crystals grew within 1 d. The two unique anions and cations are embedded in an extended water cluster network and an extensive hydrogen bonding network is formed. The complexes are arranged to form intermolecular π–π interactions between neighboring 2amp ligands. A Hirshfeld surface analysis yields a detailed picture about the intermolecular interactions. Heating the compound up to about 100 °C the crystal water molecules are removed and a new crystalline material is formed. Storing the dehydrated sample in a water atmosphere leads to reformation of the title compound.

Description: The (arylimido)vanadium(V) compound, [( p -MeOC 6 H 4 N)V(O i Pr) 3 ] was demonstrated to undergo ligand exchange reaction with one or two equivalents of 2,6-difluorophenol, affording the (arylimido)vanadium(V) compounds, [( p -MeOC 6 H 4 N)V(O i Pr) 2 (O-2,6-F 2 Ph)] and [( p -MeOC 6 H 4 N)V(O i Pr)(O-2,6-F 2 Ph) 2 ]. Their X-ray crystallographic analyses elucidated the μ-isopropoxido-bridged dimeric structures, wherein each vanadium atom has a trigonal-bipyramidal arrangement with the imido and bridging isopropoxide ligands in the apical positions. The isopropoxide ligand was selectively employed as a bridging ligand between two central vanadium atoms. On the other hand, the reaction of the (arylimido)vanadium(V) compound, [( p -MeOC 6 H 4 N)VCl 3 ] and three equivalents of lithium 2,6-difluorophenoxide gave the (arylimido)vanadium(V) compound, [( p -MeOC 6 H 4 N)V(O-2,6-F 2 Ph) 3 ]. In the crystal packing, the thus-obtained compound showed a distorted trigonal-bipyramidal environment at the vanadium atoms with the μ-phenoxido-bridged dimeric structure, wherein the 2,6-difluorophenoxide ligand was found to serve as a bridging ligand.

Description: The three cesium selenido ferrate title compounds with an Se:Fe ratio of 2:1 were synthesized from stoichiometric samples reacting elemental Cs either ( A ) with Fe and Se in a double-crucible setup (Cs[FeSe 2 ], Cs 3 [FeSe 2 ] 2 ) or ( B ) with previously prepared FeSe 2 (Cs 3 [FeSe 2 ] 2 , Cs 7 [Fe 4 S 8 ]) ( T max = 800–1000 °C). The pure Fe III ferrate Cs[FeSe 2 ] crystallizes in the Tl[FeSe 2 ] type [monoclinic, space group C 2/ m, a = 1392.95(10), b = 564.43(3), c = 737.44(6) pm, β = 119.163(5)°, Z = 4, R 1 = 0.0550]. It is thus not isotypic to all other alkali ferrates(III) A [FeS 2 ] and A [FeSe 2 ] containing chains of edge-sharing tetrahedra, but crystallizes in a t 2 subgroup of the Immm structure of Cs[FeS 2 ]. The mixed-valent chain compound Cs 3 [FeSe 2 ] 2 is isotypic to its sulfido analogue [orthorhombic, space group Pnma, a = 777.88(6), b = 1151.02(6), c = 1341.61(7) pm, Z = 4, R 1 = 0.0470]. In contrast to the isopunctal Na 3 [FeSe 2 ] 2 type K/Rb compounds the chains are only slightly corrugated. The monoclinic, likewise mixed-valent Fe II/III selenido ferrate Cs 7 [Fe 4 Se 8 ] [monoclinic, space group C 2/ c, a = 1953.79(10), b = 879.71(5), c = 1717.03(10) pm, β = 117.890(2)°, Z = 4, R 1 = 0.0816] is isostructural both to the cesium sulfido and tellurido compound. The structure contains oligomeric moieties of four edge sharing [FeSe 4 ] tetrahedra forming slightly distorted tetrahedral clusters [Fe 4 Se 8 ] 7– , which are surrounded by a cube of 26 Cs cations. Based on a structure map, the crystal chemistry of the three title compounds is discussed together with all chain/cluster ferrates of the general series A 1+ x [Fe III 1– x Fe II x Q 2 ] ( x = 0–1; A = Na, K, Rb, Cs; Q = S, Se, Te).

Description: Studies in the systems Cs–Na–Cu–Si and Cs–Na–Zn–Si yielded the novel clathrates Cs 8 Na 16 (Cu,Si) 136 and Cs 8 Na 16 (Zn,Si) 136 , both with the cubic type-II structure [space group Fd 3 m (no. 227), Pearson symbol cF 160]. The structures of the title compounds were established from single-crystal X-ray diffraction methods, confirming the complete ordering of the Cs and Na guest atoms. The framework-building Si atoms are found to be randomly substituted by Cu atoms on framework site 96 g , exclusively. In the structure of Cs 8 Na 16 (Zn,Si) 136 , the refinements indicate that the Zn and Si atoms co-occupy two of the three framework sites with notable preference for site 96 g over site 32 e . The corresponding refined compositions and unit cell parameters are as follows: Cs 8 Na 16 Cu 3.8 Si 132.2(1) [ a = 14.7583(15) Å]; Cs 8 Na 16 Zn 6.9 Si 129.1(1) [ a = 14.7682(5) Å], respectively. The type-II clathrates can be obtained only from experiments employing both Na and Cs, whereas work in the ternary Cs-Cu-Si, Cs-Zn-Si, Na-Cu-Si, and Na-Zn-Si systems failed to yield any clathrate phases. At the same conditions, exploratory studies in the K-Zn-Si and Rb-Zn-Si systems provided evidence that type-I clathrates are favored.

Description: The colorless solid NO(HSO 4 ), known as “lead-chamber crystals”, was investigated ever since its first preparation more than two centuries ago. Its overall ionic nature now is confirmed by X-ray crystallography [ Pna 2 1 , a = 7.3558(4), b = 6.8924(3), c = 7.7017(3) Å, Z = 4]. The next neighbors of the NO + cations are four hydrogensulfate oxygen atoms, forming a distorted square at a distance of about 2.5 Å from the nitrogen atom. The square pattern next to the nitrogen atom is the most widespread coordination figure about an NO + ion in a nitrosyl salt. Depending on the anion, the interaction goes along with a decrease of the N–O stretch's excitation energy.

Description: Magnesium carbonate (MgCO 3 ) hollow nanospheres and their structural and thermal properties are presented. The hollow nanospheres are prepared via a microemulsion-based synthesis using dibutylmagnesium(II) and CO 2 as the starting materials. Size, structure, and composition of the as-prepared MgCO 3 hollow nanospheres are comprehensively validated by different analytical methods (SEM, STEM, TEM, XRD, FT-IR, TG). Accordingly, they exhibit an outer diameter of 35 ± 9 nm, an inner cavity size of 17 ± 5 nm, and a wall thickness of 9 ± 3 nm. Furthermore, the as-prepared MgCO 3 hollow nanospheres exhibit a specific surface area of 90 m 2 · g –1 and pore radii with a maximum at 10–15 nm that both reflect the inner cavity. By sintering (600 °C), the MgCO 3 hollow nanospheres can be converted to MgO, which does not show a hollow-sphere structure but which still exhibits a high specific surface area (110 m 2 · g –1 ). The synthesis of MgCO 3 hollow nanospheres is generally shown for the first time.

Description: The preparation of protonated methanesulfonamide was carried out using the superacidic systems HF/AsF 5 and HF/SbF 5 . The vibrational spectroscopic characterization was supported by quantum chemical calculations performed with the PBE1PBE method using the 6-311G++(3df, 3pd) basis set. A remarkable long nitrogen–sulfur bond length of 1.804(6) Å was observed in a single-crystal X-ray structure analysis of [CH 3 SO 2 NH 3 ] + [Sb 2 F 11 ] – . It crystallizes in the orthorhombic space group P 2 1 / c with four formula units in the unit cell. Furthermore the crystal structure of CH 3 SO 2 NH 2 was revisited.

Description: The new compound {[Mn(teta)] 4 V 16 Sb 4 O 42 } n · [(H 2 O) 12 ] n ( 1 ) was synthesized under solvothermal conditions. The crystal structure features the high nuclearity [V 16 IV Sb 4 III O 42 (H 2 O)] 8– cluster anion, which consists of two rings composed of 8 edge-sharing VO 5 polyhedra. The rings are perpendicular to each other generating four niches, which are occupied by two VO 5 pyramids and two handle-like Sb 2 O 5 units. The two unique anions are each surrounded by eight Mn 2+ centered complexes via Mn–O term –V bonds. Such an expansion has never been observed in heterometal polyoxovanadate chemistry. The connection mode between cluster anions and complex cations generates two individual layers stacked onto each other. Between the layers weak Sb ··· O contacts are observed. The crystal water molecules are mainly located in the empty space between the layers. Upon heating H 2 O molecules are removed, while the crystal structure remains intact. The magnetic behavior is dominated by strong antiferromagnetic exchange interactions between the central V 4+ ions, while the interaction between the cluster anion and central Mn 2+ ions is significantly less pronounced.

Description: Four new coordination compounds, [Cd(L 1 ) 2 ] n ( 1 ), [Mn(L 1 ) 2 ] n ( 2 ), [Zn(L 1 )(NA)] ( 3 ), and [Pb(L 1 ) 2 (H 2 O)] ( 4 ) were obtained on the basis of the in-situ ligand reactions of quinoline-2-carbonitrile (QCN) and NaN 3 under solvothermal conditions. 1 and 2 are 1D isostructural chains, where the central metal atoms are six-coordinate by six nitrogen atoms in a distorted octahedron. The cycloaddition reaction of QCN and NaN 3 in the presence of hydrated ZnCl 2 occur with the aid of the ancillary ligand nicotinic acid (NA), where NA not only provides an acidic environment but also serves as an ancillary ligand. The extended structure of 3 is a 1D ladder-like polymer. Compound 4 is a mononuclear Pb 2+ compound. All the compounds were structurally characterized by X-ray crystallography and their luminescent properties were investigated in detail.

Description: Nitrogen-rich double salt ammonium 3,4-diamino-1,2,4-triazoliumstyphnate (NH 4 · DATr · TNR) ( 2 ) with good thermal stability was successfully synthesized by reacting 3,4-diamino-1,2,4-triazolium chloride aqueous solution with styphnic acid methanol solution under the reaction medium of aqueous ammonia. The title double salt was characterized by elemental analysis (EA), Fourier transformation infrared spectrum (FT-IR), and X-ray single-crystal diffraction. It crystallizes in the monoclinic crystal system with space group P 2 1 / n . Its density is 1.780 g · cm –3 . Compound 2 is thermal stable below 200 °C by the differential scanning calorimetry (DSC) test. The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. In addition, compound 2 showed low friction and impact sensitivities.

Description: The Front Cover shows molecular structures of (arylimido)vanadium(V) compounds. The (arylimido)vanadium(V) compounds bearing one or two 2,6-difluorophenoxide ligands were found to form μ -isopropoxido-bridged dimeric structures, wherein isopropoxide ligand was selectively employed as a bridging ligand between two vanadium centers. On the contrary, μ -phenoxido-bridged dimeric structure was observed in (arylimido)vanadium(V) compound bearing three 2,6-difluorophenoxide ligands. The absence of isopropoxide ligand leads to the μ -phenoxido-bridging structure in the crystal packing. More details are discussed in the article by Moriuchi, Hirao et al. on pp. 1173 ff .

Description: 3a,6a-Diaza-1,4-diphosphapentalene (DDP) reacts with hexachlorocyclopentadiene to form a stable adduct (ClC) 4 C=DDP ( 4 ). The phosphorus atom involved into coordination has a pyramidal arrangement but retains partial double bonding with carbon [1.752(3) Å]. At the same time, the P–N bond remains covalent [1.824(3) Å]. The adduct 4 is better described as a zwitterionic compound with strongly delocalized positive and negative charges. A similar zwitterionic adduct DDP=C(CN) 2 was prepared by the reactions of dichloro-DDP ( 7 ) with malononitrile in the presence of Et 3 N. DFT calculations showed that related structures are formed in the case of the substituents (ClC) 4 C=, (HC) 4 C=, (NC) 2 C=, and (MeCO) 2 C=, possessing electron-delocalizing properties. Compounds with other R 2 C groups ( R = Ph, Me, C 6 F 5 , Cl), possessing electronegative properties as well, but insufficient e-delocalization, demonstrate the noncovalent P–N bonding and a little shorter R 2 C–P bond lengths (ca. 1.70 Å).

Description: The reaction of Cd(NCS) 2 with 3-hydroxymethylpyridine (3-HMPy) leads to the formation of compounds with the composition Cd(NCS) 2 (3-HMPy) 4 ( 1-Cd ), Cd(NCS) 2 (3-HMPy) 2 ( 2-Cd ) (Cd(NCS) 2 ) 2 (3-HMPy) 3 ( 3-Cd ), and (Cd(NCS) 2 ) 3 (3-HMPy) 4 ( 4-Cd ). Compound 1-Cd consists of discrete complexes and in 2-Cd the Cd cations are linked into chains by the anionic and the organic co-ligands. In 3-Cd as well as 4-Cd the Cd cations are connected into chains by the thiocyanate anions, which are further linked into layers by the 3-HMPy co-ligands. In contrast, with Zn only one compound with the composition Zn(NCS) 2 (3-HMPy) 2 · H 2 O ( 1-Zn-H 2 O ) was characterized by single-crystal X-ray diffraction, which shows a tetrahedral coordination of the Zn cations by two thiocyanate anions and two 3-HMPy ligands. The discrete complexes are arranged to form channels, in which the water molecules are embedded. 1-Zn-H 2 O cannot be obtained phase pure and detailed investigations reveal, that additional Zn compounds with the composition Zn(NCS) 2 (3-HMPy) 2 · x H 2 O including an anhydrate ( 1-Zn ) can be obtained, which possesses a similar X-ray powder diffraction (XRPD) pattern. 1-Zn was characterized using X-ray powder diffraction analysis. Most compounds were investigated by thermoanalysis, IR and Raman as well as luminescence spectroscopy.

Description: Reaction of Cd(NCS) 2 or Zn(NCS) 2 with 3-aminomethylpyridine (3-AMPy) leads to the formation of five compounds with the compositions [Cd(NCS) 2 (3-AMPy) 2 · (3-AMPy)] n ( 1-Cd ), [ M (NCS) 2 (3-AMPy) 2 ] n [ M = Cd ( 2-Cd ), Zn ( 2-Zn )] [Cd(NCS) 2 (3-AMPy)] n ( 3-Cd ), and [Zn(NCS) 2 (3-AMPy)] 2 ( 3-Zn ). In 1-Cd the Cd cations are linked by the 3-AMPy ligands into layers that consist of rings, built up of four Cd cations and four 3-AMPy ligands. These layers are stacked to form channels, in which the 3-AMPy solvate molecules are located. In the isotypic compounds 2-Cd and 2-Zn the metal cations are also linked into layers by the 3-AMPy ligands with an identical layer topology as that in 1-Cd , but a completely different conformation of the 3-AMPy ligand. In the most 3-AMPy deficient compound 3-Cd , the Cd cations are linked by μ-1,3-bridging thiocyanate anions and 3-AMPy ligands into chains, that are further connected into layers by additional anionic ligands. In 3-Zn two Zn cations are linked by pairs of 3-AMPy ligands into discrete dimers. Thermoanalysis and X-ray powder diffraction (XRPD) investigations show that upon heating 1-Cd transforms into 2-Cd and 2-Zn into 3-Zn . The compounds 2-Cd , 3-Cd , 2-Zn , and 3-Zn present ligand-based luminescence in the blue-green spectral range with maxima between 21276 and 21795 cm –1 .

Description: Complexes and coordination polymers were obtained from trivalent lanthanide chlorides together with thiazole (thz) and the diazine ligands pyrazine (pyz) and pyrimidine (pym). The compounds [ Ln 2 Cl 6 (pyz)(thz) 6 ] · 2thz ( Ln = Tb, Er), 1 ∞ [Pr 2 Cl 6 (pyz)(thz) 6 ], and [ Ln 2 Cl 6 (pym) 2 (thz) 4 ] ( Ln = Tb, Er) could be obtained, their crystal structures, luminescence as well as thermal properties were determined. The compounds with Tb and Er show intense luminescence with a strong sensitizer effect of the ligands that can be observed by dominant ligand excitation and exclusive metal emission for VIS and NIR.

Description: The reaction of [( R 1 Sn) 3 Se 4 Cl] ( R 1 = CMe 2 CH 2 COMe) with [Pd(PPh 3 ) 2 Cl 2 ], (SiMe 3 ) 2 Se, and hydrazine hydrate yields a new Pd/Se cluster, [Pd 3 (PPh 3 ) 5 (SeH)(μ 3 -Se) 2 ][SnCl 3 ] ( 1 ). Using [( R 1 Sn) 4 Se 6 ] as reactant and varying the reaction conditions as well as the addition of (SiMe 3 ) 2 Se and hydrazine hydrate, [Pd 3 (PPh 3 ) 5 (SnCl 3 )(μ 3 -Se) 2 ][SnCl 3 ] ( 2 ) and [Pd 2 (PPh 3 ) 3 Cl{Sn R 2 Cl 2 }(μ 3 -Se) 2 ] ( 3 ) can be isolated. 3 is the first compound based on a [Pd 2 SnSe 2 ] moiety, which furthermore exhibits a functional organic group at the tin atom. Its photoluminescence and absorption spectra are discussed as well. All compounds were characterized by single-crystal X-ray diffraction, indicating a bipyramidal structure. Mass spectrometric analyses of the reaction solutions provide some insight into the formation of the clusters.

Description: Recently, deep eutectic solvents (DESs) have received great interest as sustainable reaction media for nanoscale and functional materials. We report on a new choline chloride (ChCl) and thioacetamide (TAA) based DES for the synthesis of a series of binary metal sulfides including Sb 2 S 3 , Bi 2 S 3 , PbS, CuS, Ag 2 S, ZnS, and CdS. In these reactions, the ChCl/TAA based DES serves as “all-in-one” reactant, solvent, and template or deep eutectic solvent precursor (DESP). The reaction is supposed to proceed in two steps. A metal-DES complex is first generated by adding the respective metal salts to the DES solution at a relatively low temperature. Then the metal-DES complex decomposes to form the final metal sulfides products upon heating. This method provides a simple reaction system and a general strategy to synthesize metal sulfides. Some unique shaped products, such as Sb 2 S 3 plates agglomerated by rod-like particles, hexagonal CuS single crystals, and three-dimensional hierarchical ZnS microspheres, are obtained via this method and the sizes and shapes of obtained samples can to some extent be controlled by temperature or reactant concentrations.

Description: The new compound [Rb([18]crown-6)] 3 As 15 Zn · 4NH 3 was obtained by the reaction of Rb 3 As 7 , ZnPh 2 , [18]crown-6, and [2.2.2]crypt in liquid ammonia. The black monoclinic crystals contain the (As 15 Zn) 3– anion, in which two As 7 3– cages are linked by an As–Zn unit. The anionic units are separated by cationic [Rb([18]crown-6)] + units. The analogous reaction of Rb 3 Sb 7 , ZnPh 2 , [18]crown-6, and [2.2.2]crypt yielded black triclinic crystals of the compound [Rb([2.2.2]crypt)] 4 Sb 14 Zn · 8NH 3 . This is the first antimony derivative with the ( E 14 Zn) 4– anionic motif, which consists of two nortricyclane like cages linked by a Zn atom. Quantum chemical calculations on the anionic units confirm that the electron density is mainly found at the periphery of the cluster system. This phenomenon is in accord with the observations already reported for the 1,2,3-tripnicolides.

Description: The water-stable 3D lanthanide-organic framework ( Ln -MOF) {[Eu(bci)(H 2 O)] · 2H 2 O} n ( 1 ) [H 2 bci = bis(2-carboxyethyl)isocyanurate] was synthesized under hydrothermal conditions. Compound 1 - Eu exhibits a 3D open-framework connected by Eu–(μ-O) 2 –Eu chains and bci ligands. Meanwhile, 1 - Eu exhibits highly efficient luminescent sensing for environmentally relevant Fe 3+ and SCN – ions through luminescence quenching. These results indicated that it could be utilized as a multi-responsive luminescence sensor.

Description: Two hitherto hardly characterized glycine zinc sulfates were identified in the product of a batch production process for glycine zinc sulfates of the BASF Company: Gly · ZnSO 4 · 2H 2 O and β-Gly-ZnSO 4 . The crystal structures were solved from high resolution synchrotron X-ray powder diffraction data. Gly · ZnSO 4 · 2H 2 O is the zinc analogue to an isotypic copper compound with space group P 2 1 / c (no. 14) and a = 7.8092(1) Å, b = 12.3979(2) Å, c = 8.3732(1) Å, β = 90.673(1) and V = 810.62(2) ų. The crystal structure of the hitherto unknown β-Gly-ZnSO 4 with space group P 2 1 / c (no. 14) and a = 9.2577(1) Å, b = 5.1268(1) Å, c = 12.9926(1) Å, β = 90.267(1) and V = 616.65(1) Å 3 was solved ab initio. In both crystal structures the zinc cations exhibit exotic, fivefold coordination arrangements: squared ZnO 5 -pyramids are present in the structure of the dihydrate, whereas the crystal structure of β-Gly-ZnSO 4 contains trigonal ZnO 5 -bipyramids.

Description: Two zinc(II) and nickel(II) based coordination polymers, {[Zn(bibp)(MoO 4 )](H 2 O) 2 } n ( 1 ) [bibp = 4,4′-bis(imidazol-1-yl)-biphenyl] and [Ni 2 (CN) 4 (phen) 2 ] n ( 2 ) (phen = 1,10-phenanthroline), were synthesized and structurally characterized under solvothermal conditions. Compound 1 can be viewed as the connection of the 1D W -type chain [Zn( trans -bibp)] with the MoO 4 2– anion to form a uninodal 4-connected net, whereas 2 features one-dimensional Ni II cyanide chains decorated either with linear Ni(CN) 4 side chains or with 1,10-phenanthroline ligands bound directly to the Ni II sites of the parent chain. In addition, in vitro anticancer activities of compounds 1 and 2 on four human breast cancer cells (MDA-MB-231, MDA-MB-468, SK-BR-3, and MCF7) was further determined.

Description: The deep blue, paramagnetic Cs 2 [Tc II (NO)F 5 ] is formed during reactions of pertechnetate, acetohydroxamic acid, and CsF in aqueous HF. A reaction of Cs 2 [Tc(NO)F 5 ] with BF 3 · MeOH in acetonitrile gives yellow blocks of the fluorido-bridged dimer [{Tc I (NO)(CH 3 CN) 4 } 2 F](BF 4 ) 3 . The compound is stable as solid and in acetonitrile solutions. The complex cation contains a bent μ-F – ligand and two linear nitrosyl groups.

Description: 2-Bromo- and 2-chloro-1,3,2-diazaphospholenes react with (tht)AuCl to afford isolable N-heterocyclic phosphenium (NHP) dihalido-aurates, which were characterized by analytical and spectroscopic data and in one case by a single-crystal X-ray diffraction study. The T-shaped metal coordination sphere found in the crystal consists of a pseudo-linear Au X 2 unit that is perturbed by a weakly bound NHP unit. DFT studies indicate that the subunits interact mainly through electrostatic and dispersion forces, with negligible covalent contributions, and that the phosphenium dibromido-aurate is slightly more stable than an isomeric complex with an intact bromophosphane ligand. NMR studies reveal that the NHP-Au X 2 pairs persist in solution but are kinetically labile and readily undergo halide scrambling. The hydride/fluoride exchange reaction between a secondary phosphane-AuCl complex and [Ph 3 C][BF 4 ] implies that a gold complex with an intact 2-halogeno-1,3,2-diazaphospholene ligand may be more stable than its phosphenium dihalido-aurate isomer when covalent P– X bonding contributions are strengthened.

Description: This review provides an overview of the precursor chemistry that has been developed around the phase-change material germanium-antimony-telluride, Ge 2 Sb 2 Te 5 (GST). Thin films of GST can be deposited by employing either chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques. In both cases, the success of the layer deposition crucially depends on the proper choice of suitable molecular precursors. Previously reported processes mainly relied on simple alkoxides, alkyls, amides and halides of germanium, antimony, and tellurium. More sophisticated precursor design provided a number of promising new aziridinides and guanidinates.

Description: Two ternary systems, Ge-I-P and Ge-I-As were investigated for the existence of double helical GeI Pn phases ( Pn = P, As). However, experiments in the temperature range of 673–1073 K always led to the formation of inverse type I clathrates. Optimization of the synthesis parameters resulted in phase pure samples for both clathrates on a gram scale. We found slightly varying compositions than for clathrates reported before in the two systems. Structural characterization by means of single crystal analysis and Rietveld refinement showed a defect model for the guest structures in combination with a mixed site occupancy for the host lattice sites. Both compounds reveal promising thermal conductivities and Seebeck coefficients but only small overall electrical conductivities.

Description: The quaternary chalcogenides La 3 Sn 0.5 InS 7 and La 3 Sn 0.5 InSe 7 were prepared by reactions of the elements at 1050 °C and 950 °C, respectively. They adopt noncentrosymmetric structures [hexagonal, space group P 6 3 , Z = 2; a = 10.2993(11) Å, c = 6.0921(6) Å for La 3 Sn 0.5 InS 7 ; a = 10.6533(7) Å, c = 6.4245(4) Å for La 3 Sn 0.5 InSe 7 ] in which the half-occupancy of Sn atoms within octahedral sites classifies them as belonging to the La 3 Mn 0.5 SiS 7 -type branch of the large family of quaternary rare-earth chalcogenides RE 3 M 1– x M ′ Ch 7 . The site distribution in La 3 Sn 0.5 In Ch 7 , with higher-valent Sn atoms occupying octahedral instead of tetrahedral sites, is reversed from the typical situation observed in other RE 3 M 1– x M ′ Ch 7 compounds. The ordered distribution of Sn atoms in octahedral sites and In atoms in tetrahedral sites was evaluated by bond valence sum analyses. Moreover, 119 Sn solid-state nuclear magnetic resonance (NMR) spectroscopy confirms the occupation of Sn 4+ species exclusively within octahedral sites. An optical bandgap of 1.45 eV was found for La 3 Sn 0.5 InS 7 . Band structure calculations on an ordered superstructure model of La 3 Sn 0.5 InS 7 reveal that avoidance of strongly Sn–S antibonding levels is an important driving force for the Sn deficiency.

Description: Optically active cluster compounds [W 6 Br 8 L 6 ] 2– are prepared from Cs 2 [W 6 Br 14 ], which is obtained via reduction of WBr 6 with elemental antimony in the presence of CsBr. Cesium ions and six apical bromide ligands of Cs 2 [W 6 Br 14 ] are successively replaced for n -tetrabutyl ammonium (TBA) + and ligands (L). Light yellow single-crystals of (TBA) 2 [W 6 Br 8 L 6 ] with L = CF 3 COO and C 7 H 7 SO 3 were isolated from dichloromethane solution and structurally characterized by means of X-ray single-crystal diffraction. Photoluminescence studies reveal a wide excitation range within 250 to 500 nm for both compounds and a broad emission centered at λ em,max = 735 nm (L = CF 3 COO) and 730 nm (L = C 7 H 7 SO 3 ). Oxygen dependencies of emission intensities are reported.

Description: A variety of energetic compounds combining nitro with nitrocarbamate groups were synthesized. The precursors, polynitro alcohols, were obtained by the condensation of the readily available starting material nitromethane with the small aliphatic aldehydes formaldehyde and glyoxal. The conversion into carbamates was achieved with the reactive chlorosulfonyl isocyanate (CSI) and a final nitration yielded the polynitrocarbamates. The new compounds were fully characterized, including multinuclear NMR spectroscopy, vibrational analysis, mass spectrometry, differential scanning calorimetry, and elemental analysis. The energies of formation were calculated with the GAUSSIAN program package and the detonation parameters were predicted using the EXPLO5 computer code. Due to the positive oxygen balance ( Ω CO ) of the presented compounds, their performance data as oxidizers were determined and compared to the common oxidizer ammonium perchlorate.

Description: SrZn(NCN) 2 , the first example of a ternary post-transition metal carbodiimide, was prepared by a solid-state metathesis reaction. The crystal structure was solved from PXRD data and found to adopt the orthorhombic ( Cmcm ) BaZnSO structure, a high symmetry modification of that expressed by the oxide analogue SrZnO 2 . Locally, SrZn(NCN) 2 features ZnN 4 tetrahedra and SrN 6 trigonal prisms similar to those in quarternary LiSr 2 M (NCN) 4 ( M = Al 3+ and Ga 3+ ) phases, however, the overall topologies are distinct with single chains in the former and double chains in the latter. Electronic structure calculations indicate an indirect bandgap of about 2.95 eV in SrZn(NCN) 2 , slightly lower than the experimentally observed bandgap of 3.4 eV in SrZnO 2 and consistent with a greater degree of covalency. The structural similarities between SrZn(NCN) 2 and oxychalcogenide analogues highlight the pseudochalcogenide character of NCN 2– and suggest that the title compound may serve as a template for accessing novel ternary carbodiimides featuring tetrahedrally coordinated transition metals.

Description: The title compound AuS 2 CNH 2 was prepared from an aqueous solution by reaction of dicyanidoaurate [Au(CN) 2 ] – with excess of ammoniumdithiocarbamate NH 4 S 2 CN H 2 at pH ≈ 2. The compound crystallizes in the orthorhombic space group Cmma with a = 6.4597(2), b = 12.6556(3), and c = 5.3235(1) Å. The crystal structure comprises linear S–Au–S dumbbells forming unbranched zigzag chains in combination with the dithiocarbamate ligands. The three-dimensional arrangement of the molecules is realized by aurophilic Au I –Au I and hydrogen bonding interactions, respectively. AuS 2 CNH 2 presents orange luminescence due to a broad emission band between 12000 cm –1 and 23000 cm –1 (ν = 26316 cm –1 ).

Description: Numerous arene complexes of tin(II) are well known with [AlCl 4 ] – as counterion, but none with the analogous [AlBr 4 ] – ion. Herein we report on new crystal structures containing arene complexes of tin and the tetrabromoaluminate anion obtained out of the reactions between SnBr 2 and AlBr 3 in the respective arene as solvent. Additionally, powder diffraction data and FIR spectra of the bulk products of these reactions are discussed.

Description: Through extensive research on the PbO / PbBr 2 / B 2 O 3 system, a new single crystal of yellow lead-containing oxyborate bromine, [O 2 Pb 3 ] 2 (BO 3 )Br, was grown from the melt. It crystallizes in the centrosymmetric space group Cmcm (no. 63) of the orthorhombic system with the following unit cell dimensions: a = 9.5748(8) Å, b = 20.841(2) Å, c = 5.7696(5) Å, and Z = 4. The whole structure is characterized by an infinite one-dimensional (1D) ∞ 1 [O 2 Pb 3 ] double chain, which is based on the OPb 4 oxocentered tetrahedra and considered as the derivative of the continuous sheet of OPb 4 tetrahedra from the tetragonal modification of α-PbO. The 1D ∞ 1 [O 2 Pb 3 ] double chains are further bridged by the BO 3 units through common oxygen atoms to form two-dimensional (2D) ∞ 1 [[(O 2 Pb 3 )(BO 3 )] layers, with Br atoms situated between the layers. IR spectroscopy, UV/Vis/NIR diffuse reflectance spectroscopy, and thermal analysis were also performed on the reported material.

Description: S-heterocyclic dicarboxylic acid, thiophene-2,5-dicarboxylic acid (H 2 TDC), was employed to construct a series of lanthanide-organic frameworks ( Ln OFs) with coligand acetate, formulated as [ Ln (TDC)(OAc)(H 2 O)] n [ Ln = Eu ( 1 ), Tb ( 2 ), Gd ( 3 ), Dy ( 4 ), Sm ( 5 )] under hydrothermal conditions. Structure analysis reveals that 1 – 5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC 2– and OAc – display (κ 1 -κ 1 )-(κ 1 –κ 1 )-μ 4 and (κ 2 -κ 1 )-μ 2 coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 °C. As for 1 , 2 , 4 , and 5 , the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with 5 D 4 lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H 2 TDC ligand and the 5 D 4 state energy level of Tb 3+ . The energy transfer mechanisms in compounds 1 and 2 were also discussed.

Description: Synthesis of phase-pure materials in the system Sc-Nb-O-N is challenging. In this contribution we report on the preparation of the first scandium niobium oxide nitrides via reaction of water-saturated gaseous ammonia or an ammonia-oxygen mixture with amorphous scandium niobium oxides. Two new phases were obtained: rutile-type ScNb 4 O 7 N 3 , which crystallizes in space group P 4 2 / mnm , and an anion-deficient fluorite-type Sc 2 Nb(O,N,⬜) 6 phase crystallizing in space group Fm 3 m .

Description: The cover picture shows the wet chemical synthesis of phase-pure group 14/16 semiconducting materials (ME) by scrambling reactions of bistrialkylsilylchalcogenides E(SiR 3 ) 2 with germanium, tin and lead alkoxide complexes M(OC 2 H 4 NR 2 ) 2 containing a hemilabile side-arm donor function. The reactions proceed at moderate reaction temperatures in the absence of any capping agent with elimination of the corresponding silylether. Details are discussed in the article by Monika Rusek et al. on page on page 676 ff .

Description: The synthesis of monofluorinated trimesic acid (H 3 mfBTC = 2-fluoro-1,3,5-benzene-tricarboxylic acid) described in the literature leads in fact to its monopotassium salt K(H 2 mfBTC) ( 1 ), which was identified by a single crystal structure analysis ( Pc, Z = 2). It is obtained as a single-phase product and shows good solubility in water so that from aqueous solutions fourteen new coordination polymers with Ln III cations were synthesized and structurally characterized. Depending on the size of the cations three different structure types with different water contents were observed. For Ln III = La 3+ – Nd 3+ and Sm 3+ – Gd 3+ the composition 1 ∞ [ Ln III (mfBTC) 3/3 (H 2 O) 6 ] was found and confirmed by a structural analysis ( Cc, Z = 4; CN = 9). For Ln III = Tb 3+ – Ho 3+ the composition 2 ∞ [ Ln III (mfBTC) 3/3 (H 2 O) 3 ] · H 2 O was obtained and confirmed by X-ray single crystal structure analysis ( C 2/ c, Z = 8; CN = 9). Finally, for Ln III = Er 3+ – Lu 3+ the composition 1 ∞ [ Ln III (mfBTC) 2/2 (H 2 O) 5 ] · 2H 2 O was found and again confirmed by X-ray single crystal structure analysis ( P 1 , Z = 2; CN = 8). Subtle changes of the cationic radii lead to different coordination spheres and thus to different compositions. The thermal stability of selected compounds representing all three structure types was investigated by DTA/TGA measurements. All compounds are stable up to at least 100 °C, before the release of water molecules starts. The Eu III and Tb III compounds show the expected intense red and green luminescence.

Description: The high-pressure nickel borate hydroxide NiB 3 O 5 (OH) was synthesized in a high-temperature/high-pressure reaction at 4 GPa and 1023 K using a Walker-type multianvil apparatus. Single-crystal X-ray diffraction was used to determine the structure of NiB 3 O 5 (OH). It crystallizes in the monoclinic space group P 2 1 / c (no. 14) with a = 4.3222(1), b = 9.5888(2), c = 8.5067(3) Å, and β = 90.50(1)°. Furthermore, the compound was characterized by powder X-ray diffraction, vibrational spectroscopy, and magnetic measurements. The effective magnetic moment is μ eff = 3.30(1) μ B and the Weiss constant θ P = –28.3(1) K indicates antiferromagnetic interactions in the paramagnetic regime.

Description: The coordination compounds, [Cu 2 (Htba)(tba)Cl] ( 1 ) and [Ag 2 (Htba)(tba)(NO 3 )] ( 2 ), were synthesized under solvothermal conditions by using a triazolate-carboxylate bifunctional organic ligand 4-(4 H -1,2,4-triazol-4-yl)benzoic acid (Htba). X-ray single crystal diffraction analyses for the two complexes revealed that compounds 1 and 2 exhibit one-dimensional (1D) chain structures with uncoordinated carboxylic groups, which are further connected by O–H ··· O hydrogen bonds into 3D, threefold interpenetrating supramolecular frameworks with different topologies belonging to 4-connected and (2,4)-connected nets with the (4 2 ·8 2 ·10 2 )(4 3 ·6 2 ·8) 2 (4 4 ·6 2 ) and (12 5 ·16)(12) 2 Schläfli symbols, respectively. The photoluminescent measurements reveal that both 1 and 2 exhibit bluish-purple emissions in the solid state at room temperature. In addition, the compound 2 can serve as an antenna for sensitizing the visible-emitting of the lanthanide cations to display their characteristic emissions.

Description: Recently, Brønsted acids, such as phosphoric acids, carboxylic acids, and triflic acid, were found to catalyze the reduction of phosphine oxides to the corresponding phosphines. In this study, we fully characterize the HCl, HOTf, and Me 2 SiHOTf adducts of triphenylphosphine oxide and find that the thermally stable adduct Ph 3 POH + OTf – is efficiently converted into triphenylphosphine at 100 °C in the presence of readily available hydrosiloxanes. Under the same reaction conditions, also Ph 3 POSiMe 2 H + OTf – selectively affords triphenylphosphine indicating that silylated phosphine oxides are likely intermediates in this process.

Description: Well-oriented ZnO nanorods (NRs) arrays were grown on Si, alumina, quartz, and FTO substrates through a ZnO seed layer followed by low temperature wet chemical process. The influence of sputtered ZnO seed layer thickness (100, 50, 32, and 16 nm), annealing temperature and CuO x coverage on the characteristics of ZnO NRs were investigated in this study. The crystalline structural, chemical, morphological, optical, and electrical properties of ZnO NRs arrays were studied by X-ray diffraction (XRD), field emission- scanning electron microscopy equipped by energy dispersive X-ray spectroscopy (FE-SEM/EDX), Raman scattering, UV/Vis - near IR absorption spectroscopy and current-voltage characteristic. XRD and Raman spectra measurement revealed that the synthesize ZnO displayed hexagonal wurtzite structure. The individual rod diameter, density, and orientation can be controlled by varying the seed layer thickness. The mean diameter and maximum length of ZnO NRs are around 55–66 nm and 282 nm, respectively. ZnO NRs/ ZnO thin film structure shows optical switching and negative differential resistance behavior as applicable to ON/OFF gate and memory devices.

Description: The electronical and optical properties of CdGa 2 S 4 under high pressures were studied using the full potential linearized augmented plane wave (FP-LAPW) method within the GGA and mBJ exchange correlation potentials from 0.0 to 16.92 GPa. The obtained results show that the lattice constants, bandgap values, and optoelectronic properties are sensitive to applied external pressures. The mBJ results indicate that the bandgap increases and the static dielectric constants decrease with increasing the pressure. The two none zero dielectric tensor components show considerable anisotropy between the perpendicular and parallel components. The maximum absorption for x direction in all pressures takes place in vacuum UV region. Also, the plasma frequency shifts to the higher energies with increasing the pressure for application in optical devices. The calculated results by mBJ are in close agreement with the experimental values.

Description: The phase and chemical compositions of the mineral chalcopyrite from the sulfide footwall vein in La Cantera (Zacatecas, Mexico) is examined by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and chemical ICP-OES analyses. The influence of the detected impurities on the thermoelectric parameters (i.e. thermopower, electrical and thermal conductivities) is discussed. Thermoelectric figure of merit, ZT , of the studied natural minerals is found to be of the same order of magnitude (ca. 10 –3 ) as reported for CuFeS 2 synthesized in the laboratory.

Description: Tetra- tert -butyl-P 5 -deltacyclene 5 represents one of only two asymmetric P-C cage compounds, which are available in highly enantiomerically enriched versions. This paper reports about stereoselective substitution reactions of 5 to develop the chemistry of optically active P-C cages further. Electrophilic substitution of the only secondary phosphorus atom P1 of the cage with methyl and benzyl groups was achieved with 92 % and 〉99 % de, but the yields of the reactions are limited due to competing processes. The uncatalyzed hydrophosphination reaction of a monosubstituted allene and two α,β-unsaturated carbonyl compounds with 5 proved to be the method of choice. cis -Butanone-P 5 -deltacyclene 12 is formed in 92 % yield and with 〉99 % de and cis -pentanone-P 5 -deltacyclene 13a is accessible with 〉99 % de for P1 and 92 % de for the attached carbon atom at the same time. Besides stereoselectivity, the hydrophosphination reaction of 5 performs with a good regioselectivity. The chiral cage 5 controls the stereoselectivity of its reactions for the cage elements as well as for the α position of a substituent.

Description: The synthesis and characterization of the rare earth chalcogenide aerogels NaYSnS 4 , NaGdSnS 4 , and NaTbSnS 4 is reported. Rare earth metal ions like Y 3+ , Gd 3+ , and Tb 3+ react with the chalcogenide clusters [SnS 4 ] 4– in aqueous formamide solution forming extended polymeric networks by gelation. Aerogels obtained after supercritical drying have BET surface areas of 649 m 2 · g –1 (NaYSnS 4 ), 479 m 2 · g –1 (NaGdSnS 4 ), and 354 m 2 · g –1 (NaTbSnS 4 ). Electron microscopy and physisorption studies reveal that the new materials have pores in the macro (above 50 nm) and meso (2–50 nm) regions. These aerogels show higher adsorption of toluene vapor over cyclohexane vapor and CO 2 over CH 4 or H 2 . The notable adsorption capacity for toluene (NaYSnS 4 : 1108 mg · g –1 ; NaGdSnS 4 : 921 mg · g –1 ; and NaTbSnS4: 645 mg · g –1 ) and high selectivity for gases (CO 2 /H 2 : 172 and CO 2 /CH 4 : 50 for NaYSnS 4 , CO 2 /H 2 : 155 and CO 2 /CH 4 : 37 for NaGdSnS 4 , and CO 2 /H 2 : 75 and CO 2 /CH 4 : 28 for NaTbSnS 4 ) indicate potential future use of chalcogels in adsorption-based gas or hydrocarbon separation processes.

Description: The calcium salts Ca 2 P 2 O 6 · 2H 2 O ( 1 ) and [Ca(H 2 O) 3 (H 2 P 2 O 6 )] · 0.5(C 12 H 24 O 6 ) · H 2 O ( 2 ) were prepared and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pbca and compound 2 in the monoclinic space group P 2 1 / n . The crystal structure of compound 1 consists of chains of edge-sharing [CaO 7 ] polyhedra linked by hypodiphosphate(IV) anions to form a three-dimensional network. The crystal structure of compound 2 consists of alternated layers of crown ether and water molecules and respective ionic units. Within the layers of ionic units the Ca 2+ cations are octahedrally coordinated by three monodentate dihydrogenhypodiphosphate(IV) anions and three water molecules. The IR/Raman spectra of the title compounds were recorded and interpreted, especially with respect to the [P 2 O 6 ] 4– and [H 2 P 2 O 6 ] 2– groups. The phase purity of 2 was verified by powder diffraction measurements.

Description: The zinc(II) coordination polymer Zn 2 (L) 2 (bix) 2 · 2H 2 O ( 1 ) [H 2 L = 4,4′-methylenebis(oxy)dibenzoic acid, bix = 1,4-bis(imidazole-1-yl-methylene)-benzene] was synthesized by hydrothermal reaction. The title compound was characterized by single-crystal X-ray diffraction analysis, IR spectroscopy, and elemental analysis. The crystal structure determination reveals that compound 1 displays a twofold interpenetrated 3D framework, in which the Zn atoms are connected by the H 2 L ligands into interesting right and left-handed helical chains. Topological analysis reveals that the title compound displays a (3,4)-connected (6 3 ) (6 5 · 8) topology. The solid-state luminescent spectra was studied. Furthermore, the dispersed solution of compound 1 in DMF exhibits strong fluorescent emission, which could be quenched by trace amount of nitrobenzene.

Description: Cs 23 Mn 16 O 23 was synthesized via the azide/nitrate route from mixtures of Mn 2 O 3 , CsNO 3 , and CsN 3 . This manganese(II/III) mixed-valent oxide, which contains only one Mn 3+ besides 15 Mn 2+ cations, was studied by single-crystal X-ray diffraction and magnetic susceptibility measurements. Its crystal structure [ P 1 , Z = 1, a = 1114.26(2), b = 1185.53(2), c = 1205.39(2) pm, α = 70.596(1), β = 80.377(2), γ = 83.072(2)°, R 1 = 0.033] is based on a honeycomb-like arrangement of cesium atoms, providing the space for two different types of one-dimensional polyoxomanganate anions, illustrated by the syntax Cs 23 [MnO 2 ] 4 [Mn 3 O 5 ] 4 . Magnetic susceptibility measurements indicate dominant antiferromagnetic intra-chain interactions present already at ambient temperature and long range inter-chain magnetic ordering at 11 K.

Description: The manganese(II)-palladium(II)-sulfide complex [MnCl 2 (μ 3 -S) 2 Pd 2 (dppp) 2 ] ( 2 ) was prepared from the reaction of [PdCl 2 (dppp)] with [Li( N , N '-tmeda)] 2 [Mn(SSiMe 3 ) 4 ] ( 2 ) in a 2:1 ratio under mild conditions. The new trimethylsilylthiolate complex [Pd(dppp)(SSiMe 3 ) 2 ] ( 3 ) was synthesized from the reaction of [Pd(dppp)(OAc) 2 ] with two equivalents of Li[SSiMe 3 ]; this was then used in a reaction with [Mn(CH 3 CN) 2 (OTf) 2 ] to form the manganese(II)-palladium(II)-sulfide cluster [Mn(OTf)(thf) 2 (μ 3 -S) 2 Pd 2 (dppp) 2 ]OTf ( 4 ).

Description: The cytotoxic and antimicrobial activity of a series of six copper(II) complexes with phosphate and hydroxymethyl derivatives of pyridine and benzimidazole were investigated. The complexes and the corresponding free ligands were tested against Staphylococcus aureus ATCC 6538, Staphylococcus epidermidis ATCC 12228, Pseudomonas aeruginosa ATCC 15442, Escherichia coli ATCC 25922, Proteus hauseri ATCC 13315, and Candida albicans ATCC 10231. Among the tested copper(II) complexes, compounds 2 and 5 containing 1 H -benzimidazol-2-ylmethyl diethyl phosphate and 2-(hydroxymethyl)benzimidazole as ligands, respectively, were most active and limited the growth of S. aureus, E. coli , and C. albicans by 30–60 % according to concentration and microorganism. The in vitro cytotoxic activity of the Cu II complexes and free ligands towards cancerous B16 (murine melanoma) and non-cancerous 10T1/2 (murine fibroblasts) cell lines was determined. The 10T1/2 cells were treated with the compounds at concentrations equal to IC 50 values for B16 cells. In spite of the use of relatively high concentrations of the complexes, the viability of 10T1/2 cells was very high, ca. 80 % in some cases. Stability of the Cu II complexes was evaluated in water solutions by UV/Vis spectroscopy. The copper(II) complex of 4-(hydroxymethyl)pyridine was synthesized and identified.

Description: Three three-dimensional (3D) heterometallic lanthanide-transition-metal (hetero- Ln -TM) compounds with the formula [ Ln 6 (Cu 4 Br 3 )(Cu 2 Br 2 ) 2 (Cu 2 Br)(IN) 20 (H 2 O) 12 ] · 2H 2 O [ Ln = Gd ( 1 ), Ln = Sm ( 2 ), Ln = Eu ( 3 )] based on the linkages of one-dimensional Ln organic chain and Cu m Br n units were synthesized by mixing Ln 2 O 3 with isonicotinic acid (HIN = pyridine-4-carboxylic acid) under hydrothermal condition. During the synthesis, two ligands were used: the isonicotinate (IN – ) stabilizes the cluster and links the one-dimensional Ln organic chains and Cu m Br n motif, whereas Br – anions play a very important role in the formation of the distinct Cu m Br n units. It is interesting that there are three different Cu-Br motifs: a closed four-membered ring [Cu 2 Br 2 ] subunit, a linear [Cu 2 Br] subunit, an S-sharp [Cu 4 Br 3 ] subunit. Strong fluorescence of compounds 2 and 3 suggests an efficient energy transfer from the ligand to Eu 3+ ions. The luminescent investigation indicates that 2 and 3 are excellent candidates for fluorescent materials.

Description: This study presents two new reliable simple correlations for predicting flash point of kerosene hydrocarbons using multiple linear regression method. The methodology assumes that the flash point of kerosene fuels can be expressed as a function of elemental composition and several structural parameters. The proposed correlations have determination coefficients of 0.910 and 0.977. Also, the first model has root mean square deviation (RMSD) and the average absolute deviations (AAD) of 10.6 and 8.2 K, respectively, for 111 kerosene fuels with different molecular structures as training set. The RMSD and AAD for the second improved model are 5.39 and 4.33 K, respectively. The predictive power of two correlations is checked using a cross validation method. ( R 2 = 0.977, Q 2 Ext = 0.975, and Q 2 LMO = 0.979). Also, these correlations give good predictions for further 25 kerosene fuels as test set. The proposed model can also be applied for designing novel kerosene fuels.

Description: The new zirconium bent metallocenes (COT)Zr(Cp t Bu2 )Cl ( 1 ) and (COT)Zr(Cp′′)Cl ( 2 ) were synthesized in a straightforward manner and in high yields ( 1 : 91 %, 2 : 86 %) by treatment of in situ -prepared (COT)ZrCl 2 (THF) with 1 equiv. of K(Cp t Bu2 ) or K(Cp′′), respectively (COT = η 8 -cyclooctatetraenyl; Cp t Bu2 = η 5 -1,3-di- tert -butylcyclopentadienyl; Cp′′ = η 5 -1,3-bis(trimethylsilyl)cyclopentadienyl). Subsequent reaction of 1 with 1 equiv. of phenyllithium afforded the σ -phenyl derivative (Cp t Bu2 )Zr(COT)Ph ( 3 ) as orange crystals in 83 % isolated yield. All three new compounds were structurally characterized through single-crystal X-ray diffraction.

Description: Sc 1.67 B 3 O 7 was synthesized in a high-pressure/high-temperature experiment at 3.5 GPa/1200 °C employing a Walker-type multianvil module. The compound was characterized with X-ray diffraction and vibrational spectroscopy. It crystallizes in the tetragonal, acentric space group P 4 2 1 m (no. 113) with the lattice parameters a = 6.6597(4) and c = 4.4364(3) Å. Sc 1.67 B 3 O 7 is the first ternary compound adopting the melilite-type structure and therefore the simplest representative of this manifold structure family.

Description: A new representative of rare-earth metal(III) fluoride oxoselenates(IV) derivatized with alkali metals could be synthesized via solid-state reactions. Colorless single crystals of CsSc 3 F 6 [SeO 3 ] 2 were obtained through the reaction of Sc 2 O 3 , ScF 3 , and SeO 2 (molar ratio 1:1:3) with CsBr as reactant and fluxing agent. For this purpose, corundum crucibles embedded as liners into evacuated silica ampoules were applied as containers for these reactions at 700 °C for seven days. The new quintenary compound crystallizes in the trigonal space group P 3 m 1 with a = 565.34(4) and c = 1069.87(8) pm ( c/a = 1.892) for Z = 1. The crystal structure of CsSc 3 F 6 [SeO 3 ] 2 contains two crystallographically different Sc 3+ cations. Each (Sc1) 3+ is surrounded by six fluoride anions as octahedron, while the octahedra about (Sc2) 3+ are formed by three fluoride anions and three oxygen atoms from three terminal [SeO 3 ] 2– anions. The [(Sc1)F 6 ] 3– octahedra link via common F – vertices to six fac -[(Sc2)F 3 O 3 ] 6– octahedra forming 2 ∞ {[Sc 3 F 6 O 6 ] 9– } layers parallel to (001). These layers are separated by oxygen-coordinated Cs + cations (C.N. = 12), arranging for the charge compensation, while Se 4+ cations within the layers surrounded by three oxygen atoms as ψ 1 -tetrahedral [SeO 3 ] 2– units complete the structure. EDX measurements confirmed the composition of the title compound and single-crystal Raman studies showed the typical vibrational modes of isolated [SeO 3 ] 2– anions with ideal C 3 v symmetry.

Description: The compound Me 2 AsSI can exist in two different forms, either as dimethylarsinosulfenyl iodide [or (iodothio)dimethylarsane)], Me 2 As–S–I ( A ), or as dimethylthioarsinyl iodide (or dimethylarsinothioic iodide), Me 2 As(S)–I ( B ). To confirm that the structure of the product of the reaction between Bunsen's cacodyl disulfide Me 2 As(S)–S–AsMe 2 and iodine is A and not B , the known diethylthiophosphinyl iodide (or diethylphosphinothioic iodide), Et 2 P(S)–I ( 2 ) was prepared and its hydrolytic stability and reactivity towards a variety of nitrogen, phosphorus(III), arsenic(III), oxygen, and sulfur(II) nucleophiles were studied. The results indicated that only a few reactions of 2 resembled those of A , thus strengthening the proposal that the reaction of Bunsen's cacodyl disulfide with iodine produced A and not B . A series of 31 P NMR chemical shifts of diethylthiophosphinyl moiety is also reported. Et 2 P(S)–DMAP, synthesized and isolated during the presented study, is the ethyl analogue of Me 2 P(S)–DMAP, previously described as an important molecule. In our case, Et 2 P(S)–DMAP was found to be a good intermediate for the synthesis of phosphoryl or thiophosphoryl derivatives since it was more reactive than 2 towards nucleophiles.

Description: Two simple models are introduced to predict the char yield of different polymers. The first model is based on the basis of the number of some atoms in the repeat units that may contain chemical groups/moieties such as methyl, phenyl, carbonyl, ether, amide, and ester. The second model uses some molecular fragments beside elemental composition to derive more reliable correlation. In contrast to available Quantitative Structure – Property Relationships (QSPR) methodology, there is no need to use complex molecular descriptors, computer codes and expert users. Two models were constructed on the basis of the measured char yield of 111 polymers and compared with the predicted results of group additivity method. The root mean square (RMS) deviations of the first and second models are 12.6 and 7.2, which are lower than those predicted by two group additivity methods, i.e. 16.3. The new models were tested for 11 new synthesized polymers, where the RMS values are lower than those obtained by group additivity method.

Description: The study reports the synthesis of complexes Co(HL)Cl 2 ( 1 ), Ni(HL)Cl 2 ( 2 ), Cu(HL)Cl 2 ( 3 ), and Zn(HL) 3 Cl 2 ( 4 ) with the title ligand, 5-(pyrazin-2-yl)-1,2,4-triazole-5-thione (HL), and their characterization by elemental analyses, ESI-MS ( m/z ), FT-IR and UV/Vis spectroscopy, as well as EPR in the case of the Cu II complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the Zn II ion in 4 is coordinated by the non-protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine Co II , Ni II , and Zn II complexes in 10/90 (v/v) DMSO/water solution, whereas the Cu II complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L: M = 1:1 species with Co II , Ni II and Zn II , the 2:1 species with Co II and Zn II , and the 3:1 species with Zn II . A distorted tetrahedral arrangement of the Cu II complex was suggested on the basis of EPR and Vis/NIR spectra.

Description: The selenites, Na 2 Be 3 (SeO 3 ) 4 · H 2 O and Cs 2 [Mg(H 2 O) 6 ] 3 (SeO 3 ) 4 , were synthesized under hydrothermal conditions. The crystal structures of Na 2 Be 3 (SeO 3 ) 4 · H 2 O and Cs 2 [Mg(H 2 O) 6 ] 3 (SeO 3 ) 4 were determined by single-crystal X-ray diffractions. Na 2 Be 3 (SeO 3 ) 4 · H 2 O crystallizes in the triclinic space group P 1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Å, and Z = 2, whereas Cs 2 [Mg(H 2 O) 6 ] 3 (SeO 3 ) 4 crystallizes in the monoclinic space group C 2/ m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Å, and Z = 2. Na 2 Be 3 (SeO 3 ) 4 · H 2 O features a three-dimensional open framework structure formed by BeO 4 tetrahedra and SeO 3 trigonal pyramids. Na cations and H 2 O molecules are located in different tunnels. Cs 2 [Mg(H 2 O) 6 ] 3 (SeO 3 ) 4 has a structure composed of isolated [Mg(H 2 O) 6 ] octahedra and SeO 3 trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in-between. Both compounds were characterized by thermogravimetric analysis and FT-IR spectroscopy.

Description: LaNiO 3 perovskite is an interesting precursor for Ni/La 2 O 3 catalysts for the dry reforming of methane at high temperatures. Precursors have been synthesized by co-precipitation without, with 2.5 at %, and with 5 at % Ru doping. The presence of Ru leads to a stabilization of the perovskite structure and hinders the decomposition into NiO and Ruddlesden-Popper mixed oxides La n +1 Ni n O 3 n +1 , which was observed for the Ru-free sample upon calcination at 1000 °C ( n = 3). Upon reduction in hydrogen, a mechanism involving at least two steps was observed and the first major step was identified as the partial reduction of the precursor leading to a LaNiO 2.5 -like intermediate. The second major step is the reduction to Ni metal supported on La 2 O 3 independent of the Ru content of the catalyst. In the presence of Ru, indications for Ni-Ru alloy formation and for a higher dispersion of the metallic phase were found. The catalytic activity in DRM of the catalyst containing 2.5 % Ru was superior to the catalysts with more or without Ru. Furthermore, the propensity of coke formation was reduced by the presence of Ru.

Description: The influence of the partial substitution of Ni atoms by the similarly sized but electron-richer Ge atoms with a similar electronegativity in the binary Laves phase MgNi 2 is investigated. A small degree of substitution in MgNi 2– x Ge x ( x = 0.1) leads to the change of the hexagonal MgNi 2 -type structure (C36) to the cubic C15 type, whereas higher amounts of Ge lead to the formation of the two new Laves phases Mg 2 Ni 3 Ge and MgNi 1.30(5) Ge 0.70 , which were synthesized by the direct reaction of the elements in alumina and niobium crucibles using an induction furnace. The crystal structures of the two phases were determined by single-crystal X-ray diffraction. Mg 2 Ni 3 Ge ( hR 18-MgNi 2– x Ge x , x = 0.5) crystallizes in the Y 2 Rh 3 Ge-type structure, which is an ordered variant of the cubic Laves phase MgCu 2 : space group R 3 m, a = 5.0300(7), c = 11.330(2) Å. hP 36-MgNi 2– x Ge x with x = 0.70(6) crystallizes as a superstructure of the hexagonal Laves phase MgZn 2 : space group P 6 3 / mcm, a = 8.6946(2), c = 7.8127(3) Å. MgNi 1.3 Ge 0.7 represents a new structure type. Gradual substitution of Ni by Ge in the Laves phase MgNi 2 corresponds to an increase in the valence electron concentration (VEC) in the ternary phase system and leads to the series MgCu 2 (C15 type), hR 18-Mg 2 Ni 3 Ge (superstructure of MgCu 2 type), and hP 36-MgNi 1.3 Ge 0.7 (superstructure of MgZn 2 type). The electronic structures are discussed based on band structure calculations, and the results are compared to the pristine Laves phase MgNi 2 , MgCu 2 , and MgZn 2 with VEC = 2/3, 4/3 and 2, respectively.

Description: Malononitrile reacts in superacidic solutions HF/ M F 5 ( M = As, Sb) with formation of the corresponding salts [H 2 C(CN X ) 2 ][ M F 6 ] 2 ( M = As, Sb; X = H, D). The occurrence of double protonation is strongly dependent on the stoichiometric ratio of the Lewis acid with regard to malononitrile. Deuterated species were obtained by replacing hydrogen fluoride with deuterium fluoride. The double protonated salts were characterized by vibrational spectroscopy and in the case of [H 2 C(CNH) 2 ][AsF 6 ] 2 · HF ( 3 ) by a single-crystal X-ray structure analysis. The salt crystallizes in the monoclinic space group P 2 1 / c with four formula units per unit cell. The vibrational spectra were compared to quantum chemical calculations of the free cation [(CN)H 2 C(CNH)] + .

Description: Reactions of [{ M (μ-Cl)(coe) 2 } 2 ] ( M = Rh, Ir; coe = cis -cyclooctene) with the secondary phosphane t Bu 2 PH under various molar ratios were investigated. Probably, for kinetic reasons, the reaction behavior of the rhodium species differed from that of the iridium analogue in some instances. During these studies complexes [ M Cl( t Bu 2 PH) 3 ] [ M = Rh ( 1 ), Ir ( 2 )] were isolated, and solution variable-temperature 31 P{ 1 H} NMR studies revealed that these complexes show a conformational rigidity on the NMR time scale. Spectra recorded in the temperature range from 173 to 373 K indicated in each case only one rotamer containing three chemically nonequivalent phosphanes due to the restricted rotation of these ligands about the M –P bonds and the tert -butyl substituents around the P–C( t Bu) bonds, respectively. Compound 1 showed in solution already at room temperature in several solvents a dissociation of a phosphane ligand affording the known complex [{Rh(μ-Cl)( t Bu 2 PH) 2 } 2 ] beside the free phosphane. In contrast to these findings, the iridium analogue 2 remained completely unchanged under similar conditions and exhibited, therefore, some kinetic inertness. For a better understanding of the NMR spectroscopic investigations, the molecular structure of 1 in the solid state was confirmed by X-ray crystallography.

Description: Three copper(II) complexes of the polydentate N-donor ligand [4-(4,6-bis(1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)morpholine] (L) with chlorides, nitrates, and perchlorates as anions, namely, [CuCl 2 (L)] · 0.5(MeCN) ( 1 ), [Cu(NO 3 ) 2 (H 2 O)(L)] · (MeCN) ( 2 ), and [Cu(L) 2 ](ClO 4 ) 2 · (MeCN) ( 3 ) were synthesized and structurally characterized by IR, elemental analysis and X-ray crystallographic analysis. In these complexes, the L ligand binds the copper(II) cation in the tridentate N 3 form. The coordination arrangement around the central copper(II) atom is distorted square-pyramidal in 1 but it is distorted octahedral in 2 and 3 . The interesting noncovalent interactions such as hydrogen bonds, π–π stacking, and anion–π interactions present in the solid-state structures are discussed. The crystal results reveal that the counteranions play important roles in determining the diverse structures of these complexes. Moreover, the PXRD, TG, DRS, and fluorescence properties of compounds 1 – 3 were investigated.

Description: Reactions between 5-ferrocenylisophthalic dichloride and 1,2-bis( o -aminophenoxy)ethane yield 1:1- and 2:2-cyclization products with amide linkages, which are marked as L1 and L2 , respectively. The crystal structure of the 2:2-macrocycle L2 is determined by X-ray single crystal structure analysis. Interestingly, L2 affords a folded conformation due to the intermolecular π–π interaction between two isophthaloyl groups, so as to stabilize the marcocylic conformation. The electrochemical anion sensing studies of L1 and L2 show that they have a good ability to recognize H 2 PO 4 – , and the 2:2-cyclization products ( L2 ) with two ferrocene groups, more anion binding sites, and larger cavities, give better electrochemical anion recognition results than L1 .

Description: The compounds [(η 6 - p -cymene)RuCl 2 (4-nitroaniline)] and [(η 6 - p -cymene)RuCl 2 (2-halogen-4-nitroaniline)] were synthesized and characterized by various means. The [(η 6 - p -cymene)RuCl 2 (4-nitroaniline)] and [(η 6 - p -cymene)RuCl 2 (2-fluoro-4-nitroaniline)] compounds were determined by X-ray diffraction, appearing in a distorted piano-stool type of arrangement with similar bond lengths and angles around the ruthenium. The compounds exhibited moderate to strong in vitro cytotoxicity against A549 and MCF-7 human cancer cells. Substitution of heavy halogen atom on the ortho position of para -nitroaniline weakened the cytotoxicity against both of MCF-7 and A549, except the cases of fluorine substitution for hydrogen atom regarding A549 and bromine substitution for chlorine atom regarding MCF-7, which showed minor deviation.

Description: The formation and X-ray structure analysis of the Pt IV complex [(CH 2 C{PPh 2 C 6 H 4 } 2 )PtI 2 ] is reported. The molecule possesses the orthometalated ligand (PPh 3 ) 2 C CH 2 , which serves via its C 2 fragment as an unprecedented four-electron σ donor.

Description: The system KSi-KSiH 3 stores 4.3 wt % of hydrogen and shows a very good reversibility at mild conditions of 0.1 MPa hydrogen pressure and 414 K. We followed the reaction pathways of the hydrogenation reactions of KSi and its higher homologue CsSi by in situ methods in order to check for possible intermediate hydrides. In situ diffraction at temperatures up to 500 K and gas pressures up to 5.0 MPa hydrogen gas for X-ray and deuterium gas for neutron reveal that both KSi and CsSi react in one step to the hydrides KSiH 3 and CsSiH 3 and the respective deuterides. Neither do the Zintl phases dissolve hydrogen (deuterium), nor do the hydrides (deuterides) show any signs for non-stoichiometry, i.e. all phases involved in the formation are line phases. Heating to temperatures above 500 K shows that at 5.0 MPa hydrogen pressure only the reaction 2CsSi + 3H 2 = 2CsSiH 3 is reversible. Under these conditions, KSiH 3 decomposes to a clathrate and potassium hydride according to 46KSiH 3 = K 8 Si 46 + 38KH + 50H 2 .

Description: The cover picture shows a projection of the unit cell of [Ca(H 2 O) 3 (H 2 P 2 O 6 )] ∙ 0.5(C 12 H 24 O 6 ) ∙ H 2 O along the c axis. The compound crystallizes in the monoclinic space group P2 1 / n with four formula units in the unit cell. The asymmetric unit contains one [Ca(H 2 O) 3 (H 2 P 2 O 6 )] unit, one half of a 18-crown-6 molecule and one water molecule. The crystal structure consists of alternated layers of crown ether and water molecules and respective ionic units involved in an extended hydrogen-bonding network. Within the layer of the ionic units, [Ca(H 2 O) 3 (H 2 P 2 O 6 )], each Ca 2+ cation is bridged by three anions. The Ca 2+ ion is octahedrally coordinated by O atoms of three [H 2 P 2 O 6 ] 2– anions and three water molecules. In the anionic unit, [H 2 P 2 O 6 ] 2– , the tetravalent phosphorus atoms are surrounded tetrahedrally by three oxygen atoms and one additional phosphorus atom with a P – P distance of 2.186(1) Å and P – O bond lengths from 1.493(2) to 1.581(1) Å. The discrete dihydrogen hypodiphosphate anion in staggered conformation for the P 2 O 6 skeleton has the two H atoms in cis position and exhibits, therefore, C 2 symmetry and is located at the center of inversion. The structure exhibits within the layer of the ionic units a hydrogen-bonded network, in which the [H 2 P 2 O 6 ] 2– units are joined to ribbons linked by short O – H ∙∙∙ O hydrogen bonds with distances 2.548(1) Å and 2.587(1) Å. The O – H ∙∙∙ O distances between water molecules and [H 2 P 2 O 6 ] 2– ions range from 2.745(1) to 3.033(1). Furthermore, the hydrogen-bond lengths between the 18-crown-6 ether and water molecule range from 2.857(1) to 2.899(1) Å. Details are discussed in the article by Madeline Haase and Mimoza Gjikaj on page 962 ff .

Description: The monomeric complex [Cu(L1) 2 (EDA)] ( I ) [L1 = 2,4-dinitrobenzoic acid, EDA = ethylenediamine), was solved in orthorhombic space group ( Pbca ) and characterized by elemental analysis, IR spectroscopy, powder XRD analysis, and single-crystal X-ray crystallography, in addition to photoluminescence and thermal stability investigation. The Cu 2+ ion is connecting with two L1 through monodentate mode of coordination and two nitrogen atoms from EDA. I is associated through cooperative non-covalent interactions, which are also responsible for the strengthening of the molecular assembly and organize it into a supramolecular 2D motif. Hirshfeld surface analysis was also applied to investigate the cooperative non-covalent supramolecular interactions and the results were compared with the single-crystal X-ray diffraction data. To get clear insights into the both species, electronic properties such as HOMO-LUMO, electronic chemical potential and other derived parameters were also highlighted using DFT calculations at M06-2X/ 6-31G** level of theory. The observed photoluminescence of complex I arises mainly from an excited LLCT state with small MLCT contributions (from Cu 2+ to the unoccupied p orbital of L1). The presented work exhibits another example of the utility and prosperity of such kinds of subtle information and features especially, and for complex I at molecular level, generally.

Description: A new catalyst for cross-coupling synthesis of 1,4-diphenylbutadiyne-1,3 was prepared by thermolysis of copper(II) poly-5-vinyltetrazolate. It presents heterogeneous catalyst, in which copper nanoparticles are supported on polymeric matrix surface. The catalyst is recovered, recycled, and shows high catalytic activity in cross-coupling synthesis of 1,4-diphenylbutadiyne-1,3. The reaction proceeds in aerobic conditions at room temperature in the presence of pyridine.

Description: In order to evaluate the structural and spectroscopic influence of further pyridyl ligands, e.g. as sensitizers for Ln3+-based photoluminescence, the ligand trans-1-(2-pyridyl)-2-(pyridyl)ethylene (tppe) was selected. In reactions with trivalent chlorides of the lanthanides and thiazole (thz), complexes of the formula [LnCl3(tppe)2(thz)2] were obtained for Ln = Nd, Tb, Ho, Er. They are isotypic along the series of the lanthanides and provide ligand sensitizer functions for the Ln-luminescence emission of Nd3+ and Er3+ in the near infrared region. Alike 1,2-di-(4-pyridyl)ethylene, no sensitization is observed for the 4f-based emission of Tb3+ in the visible.

Description: Quaternization of a phosphane-functionalized benzene-dithiol gave a phosphonio-decorated product which was reacted with copper and nickel salts to yield cationic metal-bis-(benzenedithiolene) complexes. Both the ligand and its complexes were fully characterized. The properties of the complexes were compared with those of previously known anionic complexes featuring identical metal coordination environments. UV-VIS and EPR studies indicate that the charge inversion induces only minor perturbations of the electronic structure of the complexes. Electro¬chemical studies indicated that the cationic species are more easily reducible and allowed to establish an unprecedented three-membered electron transfer series involving +3/+2/+1 metal oxidation states of a copper bis-dithiolene complex.

Description: The P-H functionalized Al/P-based frustrated Lewis pair (FLP) Mes(H)P-C[Al{CH(SiMe3)2}2]=C(H)-tBu (3) has the typical functionality of FLPs with Lewis acidic and basic centers in a single molecule and is able to transfer the P bound H atom to activated substrates. Nevertheless, 3 reacted with NH3 only by adduct formation with the N atom coordinated to Al (5). The relatively low basicity of the P atom prevented the for-mation of a hydrogen bridge between P and Al. Similarly, benzil and 3 afforded a simple adduct (6) with only one C=O group bonded to P and Al. The second C=O group and the P-H moiety were unaffected. 6 has two stereogenic centers, and the resulting diastereomers were identified by crystal structure determinations. Migration of the P bound H atom was only observed for substrates containing basic N atoms. Nitriles gave heterocyclic iminophosphine adducts (7) in which the N-H groups were coordinated to the Al at-oms. An isocyanate and two isothiocyanates afforded adducts via Al-X and P-C bond formation (X = O, S), and phosphaurea derivatives (8a to 8c) resulted from H shift to the exocyclic N atoms. A carbodiimide reacted with 3 by the formation of a phosphaguanidine (8d) with the imine N atom coordinated to Al. The latter reactions proceed under mild conditions and represent formally the hydrophosphination of unsaturated substrates.

Description: A trinucleating Schiff base-like ligand and its copper(II), vanadyl(IV), iron(II) and µ-oxido iron(III) complexes were synthesised and characterised in detail. In the case of the hexanuclear iron(III) complex single crystals suitable for X-ray structure analysis were obtained. For the trinuclear complexes, the m-phenlylene linkage of the phloroglucinol unit determines the magnetic exchange interactions. For the copper complex weak antiferromagnetic interactions are observed whereas the corresponding trinuclear vanadyl complex shows weak ferromagnetic exchange interactions. A competition between superexchange interactions and spin-polarisation due to differences in the symmetry of the magnetic orbitals is made responsible for this observation. In the case of the hexanuclear iron(III) complex the exchange interactions via the µ-oxido bridge dominate leading to strong antiferromagnetic interactions. The corresponding iron(II) complex is a pure high-spin complex.

Description: Nonlinear optical crystal of fluosilicate Na2SiF6 is synthesized via hydrothermal method and its structure is determined by single crystal X-ray diffraction (XRD). The space group of Na2SiF6 is P321 with cell parameters a = 8.8715(3) Å, c = 5.0484(5) Å, Z = 3, V = 344.09(4) Å3. The properties of the crystal are measured by powder XRD, infrared (IR) spectroscopy, Ultraviolet(UV)−Visible(Vis)−Near-Infrared (NIR) diffuse reflectance spectroscopy, thermogravimetric (TG) and differential scanning calorimetry (DSC) analysis. The band gap calculated using CASTEP is 7.41 eV, indicating that the cut-off edge of the Na2SiF6 crystal can be down to deep-UV energy region. The First-principles studies were performed to elucidate the structure-property relationship of Na2SiF6.

Description: Starting from stoichiometric mixtures of the elements, quaternary and quinary solid solutions (GexSn1-x)0.8(InySb1-y)0.13Te were obtained. Concerning the ratio Ge/Sn and Sb/In, respectively, lattice parameters of the metastable phases with rocksalt-type average structures approximately obey Vegard´s law. Stable phases correspond to a disordered rocksalt type at high temperature and to trigonal layered structures with van der Waal gaps at lower temperature as shown by temperature-dependent powder X-ray diffraction combined with TEM, which reveals layer-like vacancy ordering, whose extent depends on composition and thermal treatment. In the long-periodically ordered model compounds 21R-Ge0.5Sn0.5InSbTe4 and 9P-GeSnInSbTe5 studied by resonant scattering data at K-absorption edges, Sb and Sn concentrate near the van der Waals gaps. Compared to Ge0.8Sb0.13Te and Sn0.8Sb0.13Te, the simultaneous presence of In and Sn combines increased electrical conductivity with low thermal conductivity and enhanced thermoelectric properties in certain temperature ranges. Phase transitions correlate with changes of the thermoelectric properties.

Description: The combustion of mercury (II) thiocyanate to form "Pharaoh's serpents" is a spectacular reaction first described nearly two centuries ago. The large volume of distinctive yellow branches that grow from a tiny quantity of flaming reactants makes this an enchanting demonstration, often used to depict the magic of chemistry. In recent years several videos of this bizarre process have "gone viral" online. Formally, the reaction should yield a carbon nitride with the ideal formula C3N4 along with HgS. However, since early characterization attempts there has been little further study of the materials produced. Here we apply modern characterization techniques to reinvestigate the nature of the carbon nitride and its intimate relationship to the HgS produced. The HgS phase forms nanoparticles that decorate the surfaces of a C3N4 foam matrix. Both of these compounds are important wide-gap semiconductors and we propose that the "Pharaoh's serpents reaction" could be used to produce a potentially important heterojunction nanocomposite materials that could be useful optoelectronic and photocatalytic applications.

Description: The thermochemical properties of θ-Mn 6 N 5+ x and ζ-Mn 2 N 1– w were investigated by thermal analysis in inert and oxidizing atmospheres. The obtained phase transformation temperatures were used to design an in situ neutron diffraction experiment on the reaction of α-Mn and flowing NH 3 . During this in situ experiment, initially a nitrogen-poor anti-perovskite type phase ε-Mn 4 N y [0.70(3) ≤ y ≤ 0.93(3)] was formed, indicating the lowest required nitridation potential necessary for formation of this phase within the binary manganese nitrides. At slightly higher temperatures the γ- and β-type superstructured polymorphs of ζ-Mn 2 N 1– w were observed. In the same temperature region the formation of η-Mn 3 N 2 [up to 26(2) wt %] at ambient pressure conditions was noticed. For the first time, a direct evidence for the high-temperature transformation of η-Mn 3 N 2 was obtained. At 928 K the nuclear and magnetic superstructures simultaneously collapse and a cubic MnN x phase [0.56(6) ≤ x ≤ 0.70(3)] with defect rock salt structure was generated. Clear indications for the preferred transfer of N between the different above mentioned solid state nitride phases rather than direct release to the surrounding atmosphere during temperature increase were achieved from the compositions of the coexisting phases. An updated phase diagram is suggested.

Description: Large single crystals of Li 2 (Ca 3 N) 2 [Ga 4 ] and Li 2 (Sr 3 N) 2 [Ga 4 ] up to several mm in size were grown from mixtures of the respective elements and binary alkaline-earth metal nitrides in reactive lithium melts employing a modified high-temperature centrifugation-aided filtration (HTCAF) technique. The main structural features of these isotypic phases are stella quadrangula building units [Ga 4 ]Li 4/2 and octahedra (N ae 6/2 ), which form two independent interpenetrating networks. The phases crystallize in the η-carbide structure and represent diamagnetic small bandgap semiconductors. Real-space chemical bonding analysis indicates predominantly ionic bonding.

Description: Secondary interactions in which decachloro-closo-decaborate anion is involved are have been studied in solvates [Fe(phen)3][B10Cl10]∙0.875CH3CN∙0.125H2O (1), {[Fe(bipy)3][B10Cl10]}∙2Bipy∙0.5CH3CN (2), {[Fe(bipy)3]2[B10Cl10]2}∙2.25CH3CN (3), and [Fe(bipy)3]3[B10Cl10]3∙2CH3CN∙H2O (4). Structures 1-4 have been determined by X-ray diffraction analysis, and complexes 1-3 have been studied using 35Cl NQR spectroscopy. A number of CH...Cl and p...π interactions between chlorine atoms and delocalized electron density of phenyl rings or C≡N groups of acetonitrile molecules have been identified. The results obtained by the two methods were compared and relative strength of secondary interactions have been estimated.

Description: In this work we present a facile, lab scale synthesis for thorium tetrahalides ThX4 (X = Cl, Br & I). The reaction between the easily available ThO2 and AlX3 (X = Cl, Br & I) and a subsequent in situ chemical vapour transport (CVT) leads to a product of high purity which is obtained in the form of crystals or large aggregates of crystals. Their identity and purity was evidenced by X-ray powder diffraction and IR spectroscopy. The usage of ThO2 avoids, unlike earlier syntheses, the utilization of scarcely available thorium metal or of other reactants, such as CCl4, leading to impurities. Furthermore, the reaction tolerates even less pure ThO2.

Description: The sterically demanding β-diketiminate ligand Ldmp [Ldmp = HC{(CMe)N(dmp)}2, dmp = C6H3-2,6-Me2] has been used to stabilize various gallium complexes in the formal oxidation states +II and +III. The reaction of in situ generated [LdmpLi] with gallium chloride affords [LdmpGaCl2] (1), which was used as starting complex to synthesize a variety of galliumIII compounds [LdmpGaX2] (X = F (2), I (3), H (4) and Me (5). Synthesis of the binuclear complex [LdmpGaI]2 (6), with gallium in the formal oxidation state +II has been accomplished by converting "GaI" with in situ generated [LdmpLi] in toluene. All compounds have been characterized by elemental analyses, NMR, LIFDI-TOF-MS and single-crystal X-ray diffraction. Additionally DFT calculations were performed for analysis of the bonding in 6.

Description: The boroarsenate Ba[B2As2O8(OH)2] was obtained by the reaction of NH4H2AsO4, B(OH)3 and BaBr2·2H2O in the melt. Ba[B2As2O8(OH)2] was obtained as thin colourless needles, together with spherical crystals of BAsO4 as by-product, grown on a pellet of Ba[BAsO5]. The products could be separated mechanically. For neutron scattering experiments a sample was prepared with 11B(OH)3 as a starting material. The crystal structure of Ba[B2As2O8(OH)2] was determined by single-crystal X-ray diffraction and exhibits a layer structure with an unprecedented layer topology. The exact positions of the hydrogen atoms were determined using combined single crystal X-ray and powder neutron diffraction investigations. Ba[B2As2O8(OH)2] was further characterised by IR spectroscopy and EDX analysis.

Description: A series of tertiary nitriles was synthesized by alkylation of acetonitrile, primary and secondary nitriles, using alkylbromides and sodium amide in liquid ammonia. By reaction of the in situ formed organometallic Lewis acids [Cp M (CO)(PPh 3 )] + ( M = Fe, Ru) with the novel tertiary nitriles, the complexes [Cp M (CO)(PPh 3 )(N≡C–C R 1 R 2 R 3 ]BF 4 were obtained. A di-iron complex was formed with 1,6-dicyanohexane.

Description: The cyclic tert -butyl-amino alane dimer [ t Bu–N(H)AlH 2 ] 2 ( 1 ) was obtained from reaction between alane with tert -butylamine and its boranate derivative [ t Bu–N(H)–Al(BH 4 ) 2 )] 2 ( 2 ) subsequently from 1 by hydride/chloride exchange using PbCl 2 followed by reaction with LiBH 4 . Both compounds form four-membered Al 2 N 2 cycles with typical Al–N bond lengths of 1.940(5) Å ( 1 ) and 1.945(5) Å ( 2 ) as found from X-ray diffraction analysis. The tert -butyl substituents at the nitrogen atoms may be situated at the same side of the ring ( cis ) or at opposite sides ( trans ). For compound 1 both isomers are present in solution, showing particular temperature dependent NMR shifts. In the solid both compounds 1 and 2 adopt the trans arrangement. When 1 is reacted with PbCl 2 in half of the molarity ratio used for 2 , surprisingly the novel compound 3 , a zwitterion, can be obtained: [( t Bu–N)(Al–H) 3 ( t Bu–N(H)) 3 Cl((H)N– t Bu) 3 (Al–H) 2 (Al–Cl)(N– t Bu)] + [( t Bu–N)( t Bu–N(H))(AlCl 2 ) 2 ] – . X-ray structure analysis reveals that the anion is made of a tert -butyl amino aluminum dichloride dimer (central Al 2 N 2 ring) with one of the two nitrogen atoms being deprotonated. The cationic counterpart consists of three entities: (i) There is a first seco-norcubane like Al 3 N 4 basket with tert-butyl groups at the nitrogen atoms, two hydride and one chloride ligand at the aluminum atoms and three hydrogen atoms on the open side of the basket, all pointing in the same direction; (ii) There is a second similar Al 3 N 4 basket with the same substituent pattern except that all aluminum atoms have exclusively hydrogen ligands; (iii) Both baskets coordinate a central chloride through the six protons at the open nitrogen face of the baskets in such a way that the chloride lies in the center of a H 6 trigonal anti-prism [mean H–Cl–H = 56.1(9)°]. As each of the open cages has a positive charge the overall charge by combination with the chloride adds to +1. The structure of the cationic part of 3 is unprecedented in AlN polycycles.