ALBERT

Description: The lanthanide selenidogermanates [{Eu(en) 3 } 2 (μ-OH) 2 ]Ge 2 Se 6 ( 1 ), [{Ho(en) 3 } 2 (μ-OH) 2 ]Ge 2 Se 6 ( 2 ), and [{Ho(dien) 2 } 2 (μ-OH) 2 ]Ge 2 Se 6 ( 3 ) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally prepared by the reactions of Eu 2 O 3 (or Ho 2 O 3 ), germanium, and selenium in en and dien solvents respectively. Compounds 1 – 3 are composed of selenidogermanate [Ge 2 Se 6 ] 4– anion and dinuclear lanthanide complex cation [{ Ln (en) 3 } 2 (μ-OH) 2 ] 4+ ( Ln = Eu, Ho) or [{Ho(dien) 2 } 2 (μ-OH) 2 ] 4+ . The [Ge 2 Se 6 ] 4– anion is composed of two GeSe 4 tetrahedra sharing a common edge. The dinuclear lanthanide complex cations are built up from two [ Ln (en) 3 ] 3+ or [Ho(dien) 2 ] 3+ ions joined by two μ-OH bridges. All lanthanide(III) ions are in eight-coordinate environments forming distorted bicapped trigonal prisms. In 1 – 3 , three-dimensional supramolecular networks of the anions and cations are formed by N–H ··· Se and N–H ··· O hydrogen bonds. To the best of our knowledge, 1 – 3 are the first examples of selenidogermanate salts with lanthanide complex counter cations.

Description: Density functional theory calculations using the BP86 functional in combination with triple-ζ quality basis sets have been carried out for the “early-late” transition metal complexes Cl 3 M – M ′(PCl 3 ) 4 ( M = Ti, Zr, Hf; M ′ = Co, Rh, Ir) and the derivatives R 3 M – M ′L 4 ( R = Cl, NH 2 ; L = PCl 3 , PH 3 , CO). The calculations demonstrate that the metal–metal bond strength in R 3 M – M ′L 4 can be strongly influenced by the nature of the ligands R and L. The intrinsic interaction energy Δ E int and the bond dissociation energy of the M – M ′ bonds in Cl 3 M – M ′(PCl 3 ) 4 are much smaller than in the previously investigated species (H 2 N) 3 M – M ′(CO) 4 . The M – M ′ bonds become stronger in both sets of compounds when the metal atoms become heavier. The equilibrium geometries of Cl 3 M – M ′(PCl 3 ) 4 which have bipyramidal structures have C 3 symmetry. The M –Co bonds in Cl 3 Zr–Co(PCl 3 ) 4 and Cl 3 Hf–Co(PCl 3 ) 4 and to a lesser degree in Cl 3 Ti–Co(PCl 3 ) 4 are unusually long because of direct interactions between the equatorial PCl 3 groups and the group 4 atoms Zr, Hf. The analysis of the metal–metal interactions suggests that Cl 3 M – M ′(PCl 3 ) 4 has M – M ′ single bonds.

Description: A new copper(II) phosphonatobenzenesulfonate incorporating 4,4′-bipyridine (4,4′- bipy ) as auxiliary ligand has been discovered through systematic high-throughput (HT) screening of the system Cu(NO 3 ) 2 ·3H 2 O/H 2 O 3 PC 6 H 4 SO 3 H/4,4′- bipy using different solvents. The hydrothermal synthesis of [Cu(HO 3 PC 6 H 4 SO 3 )(C 10 H 8 N 2 )]·H 2 O ( 1 ) was further optimized by screening various copper(II) salts. The crystal structure of 1 was determined by single-crystal X-ray diffraction and unveiled the presence of isolated sixfold coordinated Jahn–Teller-distorted Cu 2+ ions. The isolated CuN 2 O 4 octahedra are interconnected by phosphonate and sulfonate groups to form chains along the c- axis. The organic groups, namely phenyl rings and 4,4′- bipy molecules cross-link the chains into a three-dimensional framework. Water molecules are found in the narrow voids in the structure which are held by weak hydrogen bonds. Upon dehydration, the structure of 1 undergoes a phase transition, which was confirmed by TG measurements and temperature dependent X-ray powder diffraction. The new structure of 1-h was refined with Rietveld methods. Detailed inspection of the structure revealed the directional switching of the Jahn–Teller distortion upon de/rehydration. Weak ferro-/ferrimagnetic interactions were observed by magnetic investigations of 1 , which switch to antiferromagnetic below 3.5 K. Compounds 1 and 1-h are further characterized by thermogravimetric and elemental analysis as well as IR spectroscopy.

Description: A report of the facile separation of C 2 -C 82 (3) fullerene is given, which has resulted in the isolation of isomerically pure C 82 (3) on a preparative scale, avoiding time consuming recycling procedures. By single-crystal X-ray analysis of C 82 (3)·Ni(OEP) (Nickel octaethylporphyrine) the first crystal structure containing pristine C 82 (3) has been revealed.

Description: The synthesis of 3,3′-bis(dinitromethyl)-5,5′-azo-1 H -1,2,4-triazole ( 5 ) using the readily available starting material 2-(5-amino-1 H -1,2,4-triazol-3-yl)acetic acid ( 1 ) is described. All compounds were characterized by means of NMR, IR, and Raman spectroscopy. The energetic compound 5 was additionally characterized by single-crystal X-ray diffraction and DSC measurements. The sensitivities towards impact, friction and electrical discharge were determined. In addition, detonation parameters (e.g. heat of explosion, detonation velocity) of the target compound were computed using the EXPLO5 code based on the calculated (CBS-4M) heat of formation and X-ray density.

Description: The new quinary fluoride-rich rubidium scandium oxosilicate Rb 3 Sc 2 F 5 Si 4 O 10 was obtained from mixtures of RbF, ScF 3 , Sc 2 O 3 and SiO 2 in sealed platinum ampoules after seventeen days at 700 °C. The colourless compound crystallises orthorhombically in space group Pnma with a = 962.13(5), b = 825.28(4), c = 1838.76(9) pm and Z = 4. For the oxosilicate partial structure, [SiO 4 ] 4– tetrahedra are connected in (001) by vertex-sharing to form corrugated unbranched vierer single layers {[Si 4 O 10 ] 4– } ( d (Si–O) = 158–165 pm, ∠(O–Si–O) = 103–114°, ∠(Si–O–Si) = 125–145°) containing six-membered rings. Similar oxosilicate layers with 6 3 -net topology are well-known for the mineral group of micas or in sanbornite Ba 2 Si 4 O 10 . Regarding other systems, identical tetrahedral layers can be found in the synthetic borophosphate Mg(H 2 O) 2 [B 2 P 2 O 8 (OH) 2 ] · H 2 O. The Sc 3+ cations are coordinated octahedrally by four F – and two O 2– anions. These cis -[ScF 4 O 2 ] 5– octahedra ( d (Sc–F) = 200–208 pm, d (Sc–O) = 202–205 pm) share one equatorial and two apical F – anions with others to build up slightly corrugated double chains along [010]. These are linked with the oxosilicate layers via two oxygen vertices to construct a three-dimensional framework with cavities apt to host the three crystallographically independent Rb + cations with coordination numbers of eleven, twelve and thirteen.

Description: Swedenborgite-type cobaltites and ferrites and derivatives, represent a very important class of oxides, Ln Ba M 4 O 7 and CaBa M 4 O 7 ( M = Co, Fe). They are one of the rare families of mixed valent transition metal oxides, where the transition element exhibits exclusively the tetrahedral coordination. Their complex crystal chemistry, involving closely related structures with various symmetries (orthorhombic, hexagonal cubic) and possibility of oxygen “hyperstoichiometry”, leading to Ln Ba M 4 O 7+ δ oxides is described herein, as well as their ability to exhibit structural transitions vs. temperature. It is also shown that the triangular geometry of these new strongly electron correlated systems, plays an important role in their physics, particularly in the competition that appears between the 1D magnetic ordering and the 2D magnetic frustration. The generation of new magnetodielectric properties for CaBaCo 4 O 7 is also emphasized.

Description: [Et 2 Sn(O 2 AsMe 2 ) 2 ] ( 1 ) and [Ph 2 Sn(O 2 AsMe 2 )(μ-OMe)] 2 ( 2 ) were synthesized by treatment of Et 2 SnO and Ph 2 SnS with HO 2 AsMe 2 in Methanol, respectively. The compounds were characterized by elemental analyses, vibrational spectroscopy and mass spectrometry. According to X-ray diffraction measurements compound 1 crystallizes monoclinic in space group P 2 1 / n with cell parameters a = 804.89(3), b = 987.11(5), c = 966.42(4) pm, β = 113.354(3)°. The unit cell parameters of 2 , which crystallizes in the same space group, are a = 974.4(1), b = 1463.3(1), c = 1228.9(1) pm, β = 111.324(3)°. The (SnOAsO) 4 rings of 1 are linked and form a two-dimensional network with the SnEt groups pointing into the holes of the next layer. Compound 2 occurs as a dimer with internal Sn(OMe) 2 Sn bridges in the (SnOAsO) 2 rings. The vibrational and mass spectra are given and discussed.

Description: The structure of amorphous In 2–2 x Zn x Sn x O 3 ( a -ZITO, x = 0.2, 0.3, 0.4) was investigated with transmission electron microscopy (TEM), the total scattering pair-distribution function (PDF) and X-ray absorption spectroscopy (XAS), which revealed a well-defined short-range structure that differed from the crystalline bixbyite and corundum ZITO polymorphs. The X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were used to detect InO 6 and SnO 6 octahedra and ZnO 4 tetrahedra in a -ZITO, which differ from the InO 6 , SnO 6 and ZnO 6 pseudo-octahedra that are observed in the bixbyite and corundum ZITO polymorphs. The formation of the ZnO 4 tetrahedron likely inhibits the crystallization of ZITO when synthesized under mild conditions. in situ XRD showed a gradual transition from a -ZITO to a mixture of the bixbyite and corundum ZITO polymorphs as the temperature was raised from 300 °C to 568 °C.

Description: The alkaline earth metal complex [Mg{4,5-(P(S)Ph 2 ) 2 } 2 tz} 2 (thf) 4 ] ( 2 ) and the bimetallic complexes, [ M {4,5-(P(S)Ph 2 ) 2 } 2 tz} 2 (thf)] 2 [ M = Ca ( 3 ), Sr ( 4 ), Ba ( 5 )], [SrI{4,5-(P(S)Ph 2 ) 2 tz} 2 (thf) 3 ] 2 ( 6 ), and [{BaI(4,5-(P(S)Ph 2 ) 2 tz)} 2 (thf) 7 ] ( 7 ) were prepared in good yields from the metathesis reactions of the potassium salt of 4,5-bis(diphenylthiophosphoranyl)-1,2,3-triazole [H{4,5-(P(S)Ph 2 ) 2 tz}] ( 1 ) and M I 2 ( M = Ca, Sr, Ba), whereas the tetrametallic magnesium hydroxide [Mg 2 (μ-OH){4,5-(P(S)Ph 2 ) 2 } 2 tz} 3 ] 2 ( 8 ) was obtained as the hydrolysis product from the starting material (Mg n BuCl) and 1 . The NMR study of 2 – 8 in solution suggests the formation of solvated species in CD 3 OD- d 4, whereas for 4 , 5 , and 6 a fluxional behavior is observed in CD 2 Cl 2 . The structural analyses of 3 – 5 , 6 , and 7 in solid state reveal in all cases a central core defined by M 2 N 4 heterocycle bearing M –S bonding. The degree of aggregation observed for these compounds depends significantly on the size of the metal atom as well as on the metal-ligand molar ratio employed for each reaction.

Description: Melting reactions of copper, CuI, selenium, and Bi 2 Se 3 yielded black, shiny needles of Cu 4 BiSe 4 I = Cu 4 BiSe 2 (Se 2 )I. The compound decomposes peritectically above 635(5) K and crystallizes in the orthorhombic space group Pnma with a = 960.1(1) pm, b = 413.16(3) pm, and c = 2274.7(2) pm ( T = 293(2) K). In the crystal structure, strands [BiSeSe 2/2 (Se 2 ) 2/2 ] 3– run along [010]. Therein, the bismuth(III) cation is coordinated by five selenium atoms, which form a square pyramid. The copper(I) cations are coordinated tetrahedrally by selenide, diselenide and iodide ions. Edge-sharing of these tetrahedra results in zigzag chains of copper cations with short distances of 262.7(4) pm. Enhanced dispersion of the 3 d bands, the Crystal Orbital Hamilton Populations (COHP), and disynaptic ELI-D basins indicate weakly attractive d 10 ··· d 10 interactions between the copper cations. The semiconducting properties and the calculated electronic band structure suggest an electron-precise compound. In copper-deficient Cu 3.824(8) BiSe 4 I, the Cu···Cu distances are 5 pm shorter, and Raman spectroscopy indicates the presence of diselenide(1–) radical anions besides the diselenide(2–) groups. As a result, in Cu 3.824(8) BiSe 4 I, selenium coexists in the oxidations states –II, –I, and –0.5.

Description: Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L) 2 ] ( 2 ) [L = 4-(pyridin-4-ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, powder X-ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two-dimensional square-shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (4 4 · 6 2 ) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.

Description: [ M NCl 2 (PPh 3 ) 2 ] complexes ( M = Re, Tc) react with N -[(dialkylamino)(thiocarbonyl)]- N ′-(2-hydroxyphenyl)benzamidines (H 2 L 1 ) with formation of neutral, five-coordinate nitrido complexes of the composition [ M N(L 1 )(PPh 3 )]. The products have distorted square-pyramidal coordination spheres with each a tridentate, double-deprotonated benzamidine and a PPh 3 ligand in their basal planes.

Description: A 4d–4f heterometallic coordination polymer, [AgLa(pydc) 2 ]·3H 2 O ( 1 ) (H 2 pydc = pyridine-3,4-dicarboxylic acid), has been synthesized under hydrothermal conditions, and further characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features a three-dimensional (3D) framework containing one-dimensional (1D) channels occupied by free water molecules, which is constructed from 1D inorganic heterometallic chains and linear pydc linkers. To the best of our knowledge, complex 1 represents a rare example of 3D open-framework 4d–4f heterometallic coordination polymer. Moreover, after removal of the water molecules from complex 1 , the remaining material has high thermal stability and good adsorption behavior towards nitrogen gas.

Description: The novel macrocyclic decanuclear manganese(III) 30-metallacrown-10 compound [Mn 10 ( RS -3-chmshz) 10 (DMF) 10 ] · 9DMF ( 1 ) was synthesized by self-assembly and characterized (H 3 RS -3-chmshz = N -(( R , S )-3-cyclohexenoyl)-5-methylsalicylhydrazide). Compound 1 is a 30-membered decanuclear metallamacrocycle and crystallizes in triclinic space group P 2 1 / c , in an alternating …ΔΛΔΛ…-type chiral configuration. The decanuclear systems measure ~2.6 nm in diameter and ~1.1 nm in thickness. The racemic N -( R , S )-3-cyclohexenoyl group directing into the cavity of the metallamacrocycle shows the alternate R , S chiral configuration. Magnetic measurements on the title 30-metallacrown-10 compound show weak antiferromagnetic exchange interaction.

Description: Deep blue-violet colored powder samples of Ag 2 ZnZr 2 F 14 were synthesized by heating Zn(NO 3 ) 2 ·4H 2 O, Ag and ZrOCl 2 ·8H 2 O at 300 °C under fluorine atmosphere. The crystal structure of Ag 2 ZnZr 2 F 14 was refined from X-ray powder diffraction data using the Rietveld method ( C 2/ m, a = 9.0206(1) Å, b = 6.6373(1) Å, c = 9.0563(1) Å, β = 90.44(1)°, Z = 2). The structure is derived from the isotypic Ag 3 Zr 2 F 14 by replacing only one of the two crystallographically different Ag 2+ ions with Zn 2+ ions, thus leading to discrete Ag 2 F 7 dimers. These dimers are connected via nearly linear Ag–F···F–Ag bridges with short F···F distances of 2.33 Å to form two-legged ladders. Magnetic susceptibility measurements and density functional calculations show that the two Ag 2+ ions in each Ag 2 F 7 dimer are strongly coupled antiferromagnetically.

Description: The crystal structure of EMIm diaquobis(μ-oxalato)chromate(III) (1-ethyl-3-methylimidazolium chromium(III) dioxalate dihydrate) was determined from X-ray single crystal diffraction studies. A pale violet crystal of good optical quality was used for the structure determination at –100(2) and 25(2) °C. The basic crystallographic data for the low temperature structure are as follows: triclinic symmetry, space group P , a = 7.6202(8) Å, b = 9.7668(9) Å, c = 10.7171(11) Å, α = 109.257(9)°, β = 90.494(8)°, γ = 105.685(8)°, V = 720.75(1) Å 3 . The crystal structure was solved by direct methods and refined (using anisotropic displacement parameters for all non-hydrogen atoms) to a final residual of R 1 = 0.039 for 2062 independent observed reflections [ I 〉 2σ( I )]. The compound is built up from alternating layers parallel to (010) containing (EMIm) + cations or Cr(C 2 O 4 ) 2 (H 2 O) 2 – anions, respectively. The two crystallographically independent Cr(C 2 O 4 ) 2 (H 2 O) 2 octahedra reside on centers of symmetry (Wyckoff sites 1 a and 1 f ). The corners of the octahedra consist of four oxygen atoms from two oxalate groups and two additional water molecules. EMIm + cations provide linkage between different octahedral layers by hydrogen bridging. The water molecules in turn form hydrogen bonds with adjacent octahedra within the same layer. According to DTA/TG experiments the present compound shows several thermal processes in the range between room temperature and 1000 °C. However, pyrolysis is reproducibly yielding pure inorganic composites, qualifying this novel organic-inorganic hybrid salt also as a stable precursor for nanoscalar ceramic materials. The final product consists of a distinct mixture of Cr 2 O 3 and Cr 3 C 2 in the molar ratio of 1:1. Concomittant oxide and carbide formation is an unprecedented disintegration pathway of the thermal treatment of oxalatochromates without reducing atmosphere.

Description: A comparative atomistic study of the high-pressure polymorphism in crystalline RbF and NaBr is presented. For RbF a pair potential is developed from coarse-graining DFT-LDA calculations. The results clearly indicate the intermediate role of structural motifs of B33 type. In RbF it appears as an interfacial motif, in NaBr B33 phase grows larger from an initial inset within the pristine B1 structure, highlighting the role of chemical reactivity and smooth reactivity trends in high-pressure experiments.

Description: The crystal structure of distrontium octacyanotungstate decahydrate, Sr 2 [W(CN) 8 ] · 10H 2 O, was solved using X-ray single crystal diffraction. The tungsten atom lies on a two fold axis. Eight cyanide anions create tetragonal antiprismatic coordination sphere of tungsten atom. The two edge-sharing tetragonal antiprisms of [Sr(NC) 3 (OH 2 ) 5 ], create a dimer, [Sr 2 (CN) 6 (H 2 O) 6 (μ-H 2 O) 2 ], which lies on the inversion center. One symmetry independent water molecule is located in a void of 40 Å 3 . Vibrational (FT-IR and FT-Raman spectroscopic) behavior of main structural units is discussed. It was spectroscopically confirmed that the geometry of [W(CN) 8 ] 4– anion is slightly distorted from that corresponding to “free” anion. The number of observed bands is significantly lower than that expected for C 2 point group.

Description: This paper estimates some thermochemical (in kcal mol –1 ) and detonation parameters for the ionic liquid, [emim][ClO 4 ] and its associated solid in view of its investigation as an energetic material. The thermochemical values estimated, employing CBS-4M computational methodology and volume-based thermodynamics (VBT) include: lattice energy, U POT ([emim][ClO 4 ]) ≈ 123 ± 16 kcal · mol –1 ; enthalpy of formation of the gaseous cation, Δ f H °([emim] + , g) = 144.2 kcal · mol –1 and anion, Δ f H °([ClO 4 ] – , g) = –66.1 kcal · mol –1 ; the enthalpy of formation of the solid salt, Δ f H °([emim][ClO 4 ],s) ≈ –55 ± 16 kcal · mol –1 and for the associated ionic liquid, Δ f H o ([emim][ClO 4 ],l) = –52 ± 16 kcal · mol –1 as well as the corresponding Gibbs energy terms: Δ f G °([emim][ClO 4 ],s) ≈ +29 ± 16 kcal · mol –1 and Δ f G o ([emim][ClO 4 ],l) = +24 ± 16 kcal · mol –1 and the associated standard absolute entropies, of the solid [emim][ClO 4 ], S ° 298 ([emim][ClO 4 ],s) = 83 ± 4 cal · K –1 · mol –1 . The following combustion and detonation parameters are assigned to [emim][ClO 4 ] in its (ionic) liquid form: specific impulse ( I sp ) = 228 s (monopropellant), detonation velocity ( V oD ) = 5466 m · s –1 , detonation pressure ( p C–J ) = 99 kbar, explosion temperature ( T ex ) = 2842 K.

Description: The bifunctional metalloligand bis(carboxyethylgermanium)sesquioxide, (HOOCCH 2 CH 2 Ge) 2 O 3 , was employed in the systematic high-throughput (HT) investigation of the system Zn 2+ /(HOOCCH 2 CH 2 Ge) 2 O 3 /H 2 O/C 4 H 9 OH. Two new metal-organogermanates Zn[(OOCCH 2 CH 2 Ge) 2 O 3 ] ( 1 ) and Zn 2 (O 3 GeCH 2 CH 2 COO) ( 2 ) were discovered that show two new structural motifs for this class of compounds. Whereas in compound 1 a formal intercalation in the structure of (HOOCCH 2 CH 2 Ge) 2 O 3 is observed, 2 exhibits a new layered structure composed of CGeO 3 and ZnO 4 unit linked by μ 3 -oxygen atoms. Both connectivity modes lead to dense three-dimensional framework structures.

Description: A rare tetra-yttrium-supported Krebs-type tungstoantimonate was prepared in an acidic solution at pH 2.2 and characterized by elemental analysis and IR spectroscopy. Single-crystal X-ray analysis was carried out on Na 2 [{Y(H 2 O) 7 } 4 Sb 2 W 22 O 76 ]·14H 2 O ( 1 ), which comprises a Krebs-type [Sb 2 W 22 O 76 ] 14– unit supported by four yttrium ions.

Description: The synthesis of 5,5′-diamino-3,3′-azo-1 H -1,2,4-triazole ( 3 ) by reaction of 5-acetylamino-3-amino-1 H -1,2,4-triazole ( 2 ) with potassium permanganate is described. The application of the very straightforward and efficient acetyl protection of 3,5-diamino-1 H -1,2,4-triazole allows selective reactions of the remaining free amino group to form the azo-functionality. Compound 3 is used as starting material for the synthesis of 5,5′-dinitrimino-3,3′-azo-1 H -1,2,4-triazole ( 4 ), which subsequently reacted with organic bases (ammonia, hydrazine, guanidine, aminoguanidine, triaminoguanidine) to form the corresponding nitrogen-rich triazolate salts ( 5 – 9 ). All substances were fully characterized by IR and Raman as well as multinuclear NMR spectroscopy, mass spectrometry, and differential scanning calorimetry. Selected compounds were additionally characterized by low temperature single-crystal X-ray diffraction measurements. The heats of formation of 4 – 9 were calculated by the CBS-4M method to be 647.7 ( 4 ), 401.2 ( 5 ), 700.4 ( 6 ), 398.4 ( 7 ), 676.5 ( 8 ), and 1089.2 ( 9 ) kJ · mol –1 . With these values as well as the experimentally determined densities several detonation parameters were calculated using both computer codes EXPLO5.03 and EXPLO5.04. In addition, the sensitivities of 5 – 9 were determined by the BAM drophammer and friction tester as well as a small scale electrical discharge device.

Description: The Raman spectroscopic studies on samples with the starting compositions Cs 4 [Si 2 Ge 2 ] and M 4 [Ge 2 Sn 2 ] ( M = K, Cs) verify unambiguously the presence of phases composed of the mixed cluster moieties [Si x Ge 4– x ] 4– and [Ge x Sn 4– x ] 4– ( x = 1–3) including the pure anions [ E 4 ] 4– ( E = Si, Ge, Sn). The assignment of the vibrational frequencies is supported by normal coordinate analysis (NCA). The results for the mixed cluster anions are discussed in context with their isoelectronic analogs P x As 4– x ( x = 1–3) and SbP 3 . Using the characteristic breathing frequencies, one obtains for the ratio factor of the mixed moieties κ = ν([Si x Ge 4– x ] 4– ) / ν(P x As 4– x ) = 0.79, which is in good agreement with the reported value of 0.77 for the pure cluster series [ E 4 ] 4– ( E = Si, Ge, Sn) and X 4 ( X = P, As, Sb). The experimental average force constants f (Si-Ge) = 1.01 Ncm –1 and f (Ge-Sn) = 0.77 Ncm –1 correspond to arithmetic mean of those obtained for the pure anions in the binaries M 4 E 4 ( M = K, Rb, Cs; E = Si, Ge, Sn). The phonon frequencies of binary M 4 E 4 ( M = K, Cs; E = Si, Ge, Sn) and ternary K 4 E x E ′ 4– x ( E , E ′ = Si, Ge or Ge, Sn, E ≠ E ′, x = 1, 2, 3) were calculated by using pseudopotential electronic structure method SIESTA. Excellent agreement between the calculated and experimental frequencies was obtained for the pure binaries. The theoretical results compare also well with experimental values for the mixed series [Si x Ge 4– x ] 4– , whereas for the corresponding mixed Ge-Sn species the differences between measured and calculated frequencies are greater than 10 %.

Description: Two new thio/selenidogermanates [Ni 2 (μ-teta)(teta) 2 ]Ge 4 S 10 ·H 2 O ( 1 ) and [Ni(teta) 2 ] 2 Ge 4 Se 10 ·0.5H 2 O ( 2 ) (teta = triethylenetetramine) were solvothermally synthesized and structurally characterized. Both 1 and 2 consist of discrete [Ge 4 Q 10 ] 4– (Q = S, Se) adamantane-like anions with complex cations as counterions. The [Ge 4 Q 10 ] 4– (Q = S, Se) anions are composed of four nearly tetrahedral Ge IV atoms to which are bonded four terminal Q atoms and six bridging Q atoms. Although numerous thio/selenidogermanates with complex cations have been reported, their anions are usually dimeric [Ge 2 Q 6 ] 4– (Q = S, Se) species. 1 and 2 represent the rare examples of the adamantane-like thio/selenidogermanates with complex cations. The optical absorption spectra indicate that 1 and 2 are wide-band-gap semiconductors.

Description: The organizations of neurons, axons and dendrites in brain space are described with structures of infinite types of rods using Gauss distribution mathematics. Hermitian wavelets are used to describe mechanisms of thought.

Description: Three new compounds of the dimeric cluster anion [Ge 9 –Ge 9 ] 6– were obtained from liquid ammonia solutions of the Zintl phase K 4 Ge 9 . All of them follow the general formula K n [K([2.2.2]crypt)] 6– n [Ge 9 –Ge 9 ](NH 3 ) m ( 1 : n = 4, m = 14; 2 : n = 3, m = 18; 3 : n = 2, m = 17.28) and comprise sequestered and non-sequestered K + cations in different ratios. The non-sequestered cations coordinate to the Ge 9 cages and support the covalent intercluster bond. Additionally, they are in contact with each other by varying numbers of coordinative ammonia bridges leading to arrangement of the anions. The dimensionality of the cluster arrangements correlates with the amount of sequestering molecules. Layers, double chains and single chains are observed for 1 , 2 , and 3 , respectively, according to an increase of [2.2.2]crypt) per formula unit for 1 to 3 .

Description: We have investigated the magnetic ordering and spin dynamics of the solid solution series Ba 1– x Eu x Si with 0 〈 x ≤ 1 applying X-ray diffraction, electric conductivity measurements, Mössbauer spectroscopy, muon spin depolarization, and neutron diffraction. Our results suggest a spin glass-like behavior of Ba 1– x Eu x Si for concentrations close to x = 0.3 exist. Different spin ordering phenomena are found, which are dependent on the relative europium concentrations.

Description: The new compounds Pr 8 (C 2 ) 4 Cl 5  (1), Pr 14 (C 2 ) 7 Cl 9  (2), Pr 22 (C 2 ) 11 Cl 14  (3), Ce 2 (C 2 )Cl (4), La 2 (C 2 )Br (5), Ce 2 (C 2 )Br (6), Pr 2 (C 2 )Br (7), Ce 18 (C 2 ) 9 Cl 11  (8), and Ce 26 (C 2 ) 13 Cl 16  (9) were prepared by heating mixtures of LnX 3 , Ln and carbon or in an alternatively way LnX 3 , and “ Ln 2 C 3– x ” in appropriate amounts for several days between 750 and 1200 °C. The crystal structures were investigated by X-ray powder analysis (5–7) and/or single crystal diffraction (1–4, 8, 9). Pr 8 (C 2 ) 4 Cl 5 crystallizes in space group P 2 1 / c with the lattice parameters a = 7.6169(12), b = 16.689(2), c = 6.7688(2) Å, β = 103.94(1) °, Pr 14 (C 2 ) 7 Cl 9 in Pc with a = 7.6134(15), b = 29.432(6), c = 6.7705(14) Å, β = 104.00(3) °, Pr 22 (C 2 ) 11 Cl 14 in P 2 1 / c with a = 7.612(2), b = 46.127(9), c = 6.761(1) Å, β = 103.92(3) °, Ce 2 (C 2 ) 2 Cl in C 2/ c with a = 14.573(3), b = 4.129(1), c = 6.696(1) Å, β = 101.37(3) °, La 2 (C 2 ) 2 Br in C 2/ c with a = 15.313(5), b = 4.193(2), c = 6.842(2) Å, β = 100.53(3) °, Ce 2 (C 2 ) 2 Br in C 2/ c with a = 15.120(3), b = 4.179(1), c = 6.743(2) Å, β = 101.09(3) °, Pr 2 (C 2 ) 2 Br in C 2/ c with a = 15.054(5), b = 4.139(1), c = 6.713(3) Å, β = 101.08(3) °, Ce 18 (C 2 ) 9 Cl 11 in P with a = 6.7705(14), b = 7.6573(15), c = 18.980(4) Å, α = 88.90(3) °, β = 80.32(3) °, γ = 76.09(3) °, and Ce 26 (C 2 ) 13 Cl 16 in P 2 1 / c with a = 7.6644(15), b = 54.249(11), c = 6.7956(14) Å, β = 103.98(3) ° The crystal structures are composed of Ln octahedra centered by C 2 dumbbells. Such Ln 6 (C 2 )-octahedra are condensed into chains which are joined into undulated sheets. In compounds 1–4 three and four up and down inclined ribbons alternate (4 + 4 – , 4 + 3 – 3 + 4 –,  4 + 4 – 3 + 4 – 4 + 3 – ), in compounds 8 and 9 four and five (4 + 5 – , 5 + 4 – 4 + 5 – 4 + 4 – ), and in compounds 4–7 one, one ribbons (1 + 1 – ) are present. The Ln -(C 2 )- Ln layers are separated by monolayers of X atoms.

Description: The preparation, characterisation and single-crystal XRD molecular structure determinations of the three Ru 3 carbonyl clusters attached to carbon ligands, Ru 3 (μ-H) 3 (μ 3 -CBr)(CO) 9 ( 1 ), Ru 3 (μ-H)(μ-dppm){μ-C(OMe)}(CO) 8 ( 2 ) and AuRu 3 (μ-H) 2 (μ 3 -C=C=CHPh)(CO) 10 ( 3 ) are reported, together with the structures of the tetranuclear hydrido-carbonyls Ru 4 (μ-H) 4–2 x (CO) 11+ x (PPh 3 ) ( x = 0 4 , 1 5 ).

Description: The reaction of germa- closo -dodecaborate with oneequivalent of silver halide Ag X ( X = Cl, Br) leads to the tetrameric1:1 adducts [Et 3 MeN] 8 [{AgCl(GeB 11 H 11 )} 4 ] ( 1 ) and [Et 3 MeN] 8 [{AgBr(GeB 11 H 11 )} 4 ] ( 2 ). A cubane-like structure was determined in the solid state by single-crystal X-ray diffraction. The compounds were characterized by crystal structure analysis, 11 B NMR spectroscopy and elemental analysis.

Description: We present the low-temperature synthesis of potassium hexaamido zirconate(IV) from the transition metal tetrafluoride and thealkali metal dissolved in liquid ammonia at –40 °C. Potassium hexaamido zirconate(IV) K 2 [Zr(NH 2 ) 6 ] is the first ternary amide reported for elements of group 4 of the periodic table It crystallizes with a novel structure type in the trigonal space group R c with a = 6.5422(2) Å, c = 32.824(2) Å, V = 1216.66(9) Å 3 , Z = 6 and c / a = 5.017. The structure can be derived from the K 2 PtCl 6 type. The compound contains discrete D 3 -symmetric [Zr(NH 2 ) 6 ] 2– anions which differ significantly from octahedral shape. Quantum chemical calculations show the distortion to arise from a splitting of degenerate d-orbitals on the zirconium atom leading to a significant gain in energy.

Description: The heterocubane-like molecules [ t Bu 2 PhSiESn] 4 (E = P ( 2 ), As ( 3 )) and [(Me 3 Si) 3 SiP M ] 4 ( M = Sn ( 4 ), Pb ( 5 )) were obtained by the reaction of primary silyl phosphines or -arsines with M {N(SiMe 3 ) 2 } 2 . Likewise, the reactions of the miscellaneously substituted arsine (Me 3 Si) 3 SiAs(SiMe 3 ) 2 ( 1 ) with M Cl 2 yielded the heterocubane species [(Me 3 Si) 3 SiAs M ] 4 ( M = Sn ( 8 ), Pb ( 9 )). The unique cage compounds [( t Bu 2 PhSiAs) 4 Sn 3 LiOEt 2 ] – [Li(Et 2 O) 4 ] + ( 6 ) and [( t Bu 2 PhSiAsSn) 4 SnCl(Bu)] 4 ( 7 ) could be obtained in a metathesis reaction of SnCl 2 with the lithiated silylarsine t Bu 2 PhSiAsLi 2 in different stoichiometric percentages.

Description: The pnictides EuCd 2 X 2 ( X = P, As, Sb) and YbCd 2 Sb 2 were synthesized from the elements or a EuCd 2 precursor in tantalum tubes. The samples were characterized by powder X-ray diffraction. The structure of EuCd 2 As 2 was refined on the basis of single-crystal X-ray diffractometer data: CaAl 2 Si 2 type, P m 1, a = 444.99(9), c = 735.0(1) pm, wR 2 = 0.0372, 200 F 2 values and 10 variables. The two-dimensional [Cd 2 X 2 ] networks consist of edge-sharing Cd X 4/4 tetrahedra. The networks are separated and charge-balanced by the europium and ytterbium atoms. Redetermination of the magnetic properties revealed divalent europium and ytterbium. YbCd 2 Sb 2 is diamagnetic. For the europium compounds only one magnetic phase transition is evident, i.e. T C = 11.6 K for EuCd 2 P 2 , T N = 9.5 K for EuCd 2 As 2 , and T N = 7.4 K for EuCd 2 Sb 2 . 151 Eu Mössbauer spectra show full magnetic hyperfine field splitting at 4.2 K. A transferred hyperfine field of 7.1 T is evident in the 4.2 K 121 Sb spectrum of EuCd 2 Sb 2 .

Description: Reactions of the ligand 2 - MTPP [2-MTPP = 2-(methylthio)-4-(pyridin-2-yl)pyrimidine] with AgNO 3 and CuI produced dinuclear silver(I) ( 1 ) and copper(I) ( 2 ) complexes, respectively. Both complexes adopt a chair-like structure in which two 2 - MTPP ligands and two metal ions are joined together through M –N and M –S coordination bonds. The luminescence properties of both complexes were investigated in solid state at room temperature.

Description: Clathrates of the general formula Sn 24– x – δ In x As 22– y I 8 have been synthesized with x max = 10.7. They crystallize in the clathrate-I type of crystal structure, space group Pm n , with the cubic unit cell parameter ranging from a = 11.088 ( x = 0) to a = 11.343 ( x = 10.7) Å. The crystal structure refined for five compositions with different indium contents revealed that despite the linear dependence of the unit cell parameter upon x the details of the crystal structure change twice upon varying the indium contents. These changes occur without altering the space group and show up in positional disorder of atoms within the framework and the concomitant change of the coordination of part of tin atoms from 3+2 to 3+3, which is additionally confirmed by the Mössbauer spectroscopy data. In general, these changes reflect the transition from the Sn 24 P 19.3 I 8 structure type for high indium contents to the Sn 20.5 As 22 I 8 structure type for low indium contents. It is shown that the Sn 24– x – δ In x As 22– y I 8 clathrates have n -type conductivity with high values of the Seebeck coefficient ranging from –322 to –594 μV·K –1 at room temperature. They display an abnormally low thermal conductivity at 293 K, from 0.36 to 0.57 W·m –1 ·K –1 . The calculated thermoelectric figure-of-merit for Sn 24– x– δ In x As 22– y I 8 has its room-temperature maximum at 0.041 for x = 6.5.

Description: Phenyl bis(2-pyridyl)phosphine [PhP(2-py) 2 ] and its silver nitrate complex of formula [Ag 2 (μ-(PhP(2-py) 2 ) 2 (NO 3 ) 2 ] ( 1 ) were synthesized and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and computational studies. The silver(I) complex 1 with a 1:1 metal-ligand molar ratio is dinuclear cluster with silver atoms in same environments. Biological studies, carried out in vitro against wide range of gram positive and gram negative bacteria, have shown that the free [PhP(2-py) 2 ] ligand and its silver complex show distinct differences in the biological properties.

Description: Treatment of the tetraalkyldigallium compound R 2 Ga–Ga R 2 [ 1 , R = CH(SiMe 3 ) 2 ] with two equivalents of carboxylic acid hydrazides (4-trifluormethylbenzhydrazide, 2-fuoric acid hydrazide and 2-chlor-6-hydrazineisonicotinic acid hydrazide) afforded new digallium species by the release of CH 2 (SiMe 3 ) 2 . The intact Ga–Ga bonds of the products ( 2 to 4 ) are terminally coordinated by two chelating hydrazide ligands via NH 2 groups and the carbonyl oxygen atoms. Interesting supramolecular aggregates are formed in the solid state, which contain dimeric formula units of the digallium species connected via a complex system of hydrogen bonds. Two ether molecules are additionally coordinated to terminal N–H functions. Phenylphosphinic acid and 1 gave the analogous substituent replacement reaction with the formation of a dimeric tetragallium compound ( 5 ). Its two Ga–Ga bonds are in a perpendicular arrangement with four phosphinate ligands in the bridging positions. Oxidation of the gallium atoms and insertion of an N=N double bond into the Ga–Ga bond was observed upon treatment of 1 with azodicarbonamide.

Description: The palladium(II) and platin(II) 1,1-dicyanoethylene-2,2-dithiolates [(L–L) M {S 2 C=C(CN) 2 }] ( M = Pd: L–L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L–L) M Cl 2 ] and K 2 [S 2 C=C(CN) 2 ] or from [(PPh 3 ) 2 M {S 2 C=C(CN) 2 }] and the bisphosphane. Moreover, [(dppe)Pt{S 2 C=C(CN) 2 }]was obtained from [(1,5-C 8 H 12 )Pt{S 2 C=C(CN) 2 }] and dppeby ligand exchange. The 1,1-dicyanoethylene-2,2-diselenolates[(dppe) M {Se 2 C=C(CN) 2 }] ( M = Pd, Pt) were prepared from[(dppe) M Cl 2 ] and K 2 [Se 2 C=C(CN) 2 ]. The oxidation potentials of the square-planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S 2 C=O)] with TCNE led to a ligand fragment exchange and gave the 1,1-dicyanoethylene-2,2-dithiolate [(dcpe)Pd{S 2 C=C(CN) 2 }] in good yield.

Description: The indides Eu 2 Pd 2 In and Eu 2 Pt 2 In were synthesized from the elements in sealed tantalum tubes in an induction furnace. The samples were characterized by powder X-ray diffraction. The structures were refined on the basis of single-crystal X-ray diffractometer data: HT-Pr 2 Co 2 Al type, C 2/ c , a = 1035.7(2), b = 592.9(1), c = 823.6(2) pm, β = 104.26(1) °, wR 2 = 0.026, 1075 F 2 values, 25 variables for Eu 2 Pd 2 In and a = 1017.2(2), b = 588.7(1), c = 826.5(1) pm, β = 103.76(1) °, wR 2 = 0.062, 706 F 2 values, 25 variables for Eu 2 Pt 2 In. The indium atoms have four platinum (palladium) neighbors in strongly distorted tetrahedral coordination at Pt–In and Pd–In distances ranging from 273 to 275 pm. These InPd 4/2 and InPt 4/2 units are condensed via common edges to infinite InPd 2 and InPt 2 chains, which are surrounded by the europium atoms. The chains form the motif of hexagonal rod packing.

Description: A new metal-organic network [Co 3 (tbip) 3 (H 2 O) 4 ] · 2H 2 O ( 1 ) (H 2 tbip = 5-tert-butyl-isophthalic acid) was synthesized through the ionothermal reaction of H 2 tbip, cobalt nitrate, and [bmim]Br ionic liquid ([bmim]Br = 1-butyl-3-methylimidazolium bromide). It exhibits a three-dimensional (3D) framework with NaCl topology based on trinuclear cobalt(II) clusters as nodes. The magnetic studies show that there exist antiferromagnetic interactions between the Co II ions.

Description: Three novel 5- R -tetrazolato complexes ( R = Me, Ph, 4-Py), namely [Zn 2 (MeCN 4 ) 4 (DMSO) 2 ] ( 1 ), [Cu 2 (PhCN 4 ) 4 (en) 2 ] · 2DMSO ( 2 ), and [Cu(4-PyCN 4 ) 2 (DMSO) 2 ] · 4DMSO ( 3 ), were isolated as unexpected products under attempts to prepare heterometallic tetrazolates using a direct synthesis strategy in the Cu 0 -ZnO-en-RCN 4 H-DMSO system (en = ethylenediamine). The prepared compounds were characterized by elemental, single-crystal X-ray, and thermal analyses, and IR spectroscopy. Variation of the 5-substituent of the tetrazole ring causes different composition of complexes 1 – 3 and diverse coordination modes of 5- R -tetrazolato ligands. Complex 1 is a 3D coordination polymer due to N1,N4-bridging of 5-methyltetrazolato anions. Complex 2 , with en as a coligand, has a dinuclear structure with two copper atoms linked together by two 5-phenyltetrazolato ligands by tetrazole N2,N3 bridges. Complex 3 represents a 2D coordination polymer, formed due to 5-(4-pyridyl)tetrazolato bridges between adjacent copper atoms (with the tetrazole and pyridine rings nitrogen atoms as coordination centers). DMSO molecules, included in all the compounds, are solvate and/or coordinated ones.

Description: The reaction of [1,3-bis(2-ethoxy)benzene]triazene, [ HL ], with Hg(SCN) 2 and Hg(CH 3 COO) 2 , resulted in the formation of the complexes [Hg L (SCN)] ( 1 ) and [Hg L 2 ] · CH 3 OH ( 2 ). They were characterized by means of X-ray crystallography, CHN analysis, FT-IR, 1 H NMR, and 13 C NMR spectroscopy. The structure of compound 1 consists of two independent complexes in which the Hg II atoms are stacked along the crystallographic a axis to form infinite chains. Each Hg II atom is chelated by one L ligand and one SCN ligand, whereas in compound 2 , the Hg II atom is surrounded by two L ligands. In addition, 1D chains formed by metal–π interactions are connected to each other by C–H ··· π stacking interactions in the structure of 1 , which results in a 2D architecture. An interesting feature of compound 2 is the presence of C–H ··· π edge-to-face interactions.

Description: Two novel 3D lead(II)-azido and -thiocyanato coordination polymers with isonicotinate acid N -oxide (INO) as the coligand were synthesized and characterized by elemental analysis, IR, and 1 H NMR spectroscopy and were also studied using X-ray crystallography technique. These complexes have the formulas [Pb(INO)(NCS)] n ( 1 ) and [Pb(INO)(N 3 )(H 2 O)] n ( 2 ).

Description: A novel V IV -Ni II heterodinuclear complex [VO(cat) 2 ][Ni(1,2-PDA) 2 H 2 O] ( 1 ) (cat = catechol; 1,2-PDA = 1,2-propane diamine) was synthesized at low temperature (10 °C) and characterized by IR spectroscopy and X-ray diffraction. A novel Ni–O=V structure exists in the complex, the vanadyl–catechol moiety and the nickel–diamine moiety are connected by an oxygen bridge; all molecules are further assembled into crystallites by O–H ··· O hydrogen bonds.

Description: Sodium and potassium methyl(nitroso)amide ( M [CH 3 N 2 O], M = Na ( 1 ), K ( 2 )) were prepared by the reaction of monomethylhydrazine with iso-pentyl nitrite or n -butyl nitrite and a suitable metal ethoxide ( M [CH 3 CH 2 O], M = Na, K) in an ethanol-ether mixture. The reaction of monomethylhydrazine with a small excess of iso-pentyl nitrite or n -butyl nitrite and in the absence of a metal ethoxide led to the formation of N -nitroso- N -methylhydrazine (CH 3 (NO)N–NH 2 , ( 3 )). Alternatively, compound 3 was prepared by the amination reaction of 1 or 2 using the sodium salt of HOSA in ethanol solution. Compounds 1–3 were characterized using elemental analysis, differential scanning calorimetry, mass spectrometry, vibrational (infrared and Raman) and UV spectroscopy and multinuclear ( 1 H, 13 C and 15 N) NMR spectroscopy. For compounds 1–3 , several physical and chemical properties of interest and sensitivity data were measured and for compound 3 thermodynamic and explosive properties are also given. Additionally, the solid-state structure of compound 3 was determined by single-crystal X-ray analysis and the structures of the cis - and trans -[CH 3 N 2 O] – anions and that of 3 were optimized using DFT calculations and used to calculate the NBO charges.

Description: . Two cadmium(II) entangled frameworks, Cd(BIPA)(bpe) 1.5 ( 1 ) and Cd(BIPA)(bpp)(H 2 O) ( 2 ), were prepared by hydrothermal reactions based on rigid 5-bromoisophthalic acid (H 2 BIPA) and two flexible bipyridyl ligands 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp). The complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 is a rare example of a polycatenated array of 1D nanotubes, whereas complex 2 exhibits a three-dimensional twofold interpenetrating diamondoid network. The analysis results reveal that the flexibility of the bipyridyl ligands plays a significant role in the structure of the final products. Moreover, the luminescent properties of the complexes were investigated.

Description: The disproportionation reaction of the subvalent metastable halide SnBr proved to be a powerful synthetic method for the synthesis of metalloid cluster compounds of tin. Hence the neutral metalloid cluster compound Sn 10 [Si(SiMe 3 ) 3 ] 6 ( 1 ) was synthesized from a reaction of a SnBr emulsion with LiSi(SiMe 3 ) 3 . Using the phosphane P n Bu 3 as a donor component during the synthesis of the monohalide solution, an isolable Sn I halide solution is obtained. The reaction of such an isolable SnCl solution with LiSi(SiMe 3 ) 3 gives the anionic metalloid cluster compound {Sn 10 [Si(SiMe 3 ) 3 ] 5 } – ( 5 ) in 63 % yield, where only five tin atoms are bound to one ligand and where a centaur polyhedral arrangement of the ten tin atoms is present. Due to the open structure 5 might be used for further applications in the field of subsequent build-up reactions.

Description: Triplet fluoro sulfonyl nitrene, FS(O) 2 N ( X 3 A") was generated by ArF excimer laser irradiation ( λ = 193 nm) of FS(O) 2 N 3 isolated in solid noble gas matrices. The novel nitrene was characterized by IR ( 15 N-, 18 O-, and 34 S-labeling), UV/Vis, and EPR spectroscopy. The elusive sulfinyl nitrite, FS(O)NO, was formed in a spin-forbidden reaction upon photolysis ( λ 〉 320 nm) of triplet FS(O) 2 N. Triplet-singlet intersystem crossing (ISC) was found to compete with a spin-allowed fragmentation of the sulfonyl nitrene, which yields SO 2 + FN ( 3 Σ – ) and FNO + SO ( 3 Σ – ). Guided by DFT calculations the complex photo-decomposition of FS(O) 2 N ( X 3 A") is discussed.

Description: In celebration of Rudolf Hoppe's 90th birthday, three developments in solid state chemistry that have occurred over his tenure are personally recalled: (1) The recognition that long-range orbital order-disorder transitions introduce cooperative electron-lattice interactions has (a) accounted for numerous phase transitions in solids, (b) led to formulation of the rules for the sign, ferromagnetic vs. antiferromagnetic, of interatomic spin-spin interactions, and (c) provides a rationale for single-ion magnetostriction and magnetocrystalline anisotropy in transition-metal compounds. Moreover, the further recognition that short-range cooperative orbital ordering extends to temperatures well above the long-range orbital ordering temperature or critical concentration of orbitally degenerate cations has (a) led to the introduction of chemical inhomogeneties into a single crystallographic phase to achieve a technical objective and (b) consideration of their role in determining the sign of spin-spin interactions in a paramagnetic phase containing orbital fluctuations. (2) Exploration of the transition from localized to itinerant 3d-electron behavior in transition-metal oxides showed it to be first-order, which has allowed interpretation of (a) charge-density waves in single-valent systems and (b) dynamic phase segregations in mixed-valent systems to be manifestations of a different type of long-range vs. short-range cooperative electron-lattice coupling. (3) The study of Li-insertion chemistry has led (a) to Li-ion rechargeable batteries, (b) an appreciation of the influence of counter cations in solids on d -electron redox energies, and (c) the concept of Fermi energy pinning and its consequences as the energy of a d- electron couple in a transition-metal compound descends across the top of the anion- p bands.

Description: 1-Isopropylidene-2-methylhydrazine ( 1 ), 1-isopropylidene-2-hydroxyethylhydrazine ( 2 ) and 1-isopropylidene-2-formylhydrazine ( 3 ) were synthesized by reaction of the corresponding hydrazine with an excess of acetone in the presence of a drying agent (anhydrous sodium sulfate or barium oxide). All compounds 1 – 3 were characterized by elemental analysis, coupled gas chromatography-mass spectrometry (GC–MS), multinuclear NMR spectroscopy ( 1 H, 13 C and 15 N) and vibrational spectroscopy (infrared and Raman). Compounds 1 and 2 are liquid at room conditions and their density was measured by means of a picnometer, however, (at room conditions) compound 3 is a solid and its crystal density and structure were determined by low temperature X-ray diffraction techniques (monoclinic, P 2 1 / n , Z = 4, a = 5.666(1) Å, b = 6.254(1) Å, c = 15.277(4) Å, β = 91.30(2)°, V = 541.2(2) Å 3 ). The structure of hydrazone 3 is discussed in detail and compared to that of monoformylhydrazine. Finally, the (gas phase) structure of compound 3 was optimized using DFT calculations (B3LYP/6-31+G(d,p)) and its NBO charges are reported.

Description: The first fully characterized phase in the Nb-Ru-B system, Nb 3 Ru 5 B 2 , was successfully synthesized as polycrystalline powders as well as single crystals and characterized by EDX analysis and X-ray diffraction methods. It is the first ternary phase of the type A 3 T 5 B 2 adopting the Ti 3 Co 5 B 2 structure type and containing a group eight transition metal at the T sites. According to COHP bonding analysis the Nb–Nb interactions between two pentagonal prisms are strongly bonding and thus weaken the Nb–Ru interactions, which become significantly weaker than those found in the tetragonal prisms. Furthermore a deep pseudogap is found around the Fermi Level of the calculated DOS and the phase is predicted to be a metallic conductor as expected for this metal-rich boride.

Description: Ca 2 (PO 2 NH) 4 · 8H 2 O was obtained as single-phase crystalline powder starting from aqueous solution of K 4 (PO 2 NH) 4 · 4H 2 O and Ca(NO 3 ) 2 · 4H 2 O. A small fiber-like specimen has been used for single-crystal X-ray structure determination. In the structure of Ca 2 (PO 2 NH) 4 · 8H 2 O ( Pbcn (no. 60), a = 1700.6(3), b = 1069.3(2), c = 963.2(2) pm, Z = 4) there are (PO 2 NH) 4 4– ions in saddle conformation which are interconnected by N–H ··· O hydrogen bonds forming infinite columns running along [001]. These columns are hold together by a complex hydrogen bonding network with crystal water molecules involved. The FTIR spectrum of the title compound has been measured and the relevant bands were assigned. 31 P solid-state NMR investigations yielded three resolved resonances with chemical shift values of –3.1, –4.9 and –7.9 ppm. DTA / TG data are also discussed.

Description: Two new metal-organic coordination polymers[Eu( m -BDC) 1.5 (MOPIP) · 1/2H 2 O] n ( 1 ) and [Co( m -BDC)(MOPIP) 2 · 2H 2 O] n ( 2 ) [ m -H 2 BDC = benzene-1,3-dicarboxylic acid, MOPIP = 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline] were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The coordination polymers crystallize in monoclinic space group P 2 1 / m for 1 ( 2 : P 2 1 / n ), with a = 9.779(2), b = 18.242(4), c = 17.146(3) Å, β = 106.41(3)° for 1 , and with a = 8.2153(16), b = 27.974(6), c = 17.974(4) Å, β = 100.40(3)° for 2 . The crystal structure of complex 1 is a zipper-like chain of octacoordinate Eu 3+ ions, in which Eu 3+ ions are bridged in two coordination modes by m -BDC 2+ ligands and decorated by MOPIP ligands. The molecular structure of complex 2 consists of a hexacoordinte Co 2+ atom, which generates a slightly distorted octahedral arrangement, and assembles into three-dimensional supramolecular nets by π ··· π stacking interactions. Additionally, these two compounds show strong fluorescence in the solid state at room temperature. Natural bond orbital (NBO) analysis is performed by using the NBO method built in Gaussian 03 Program. The calculation results show a weak covalent interaction between the coordinated atoms and metal ions.

Description: The reaction of ReCl 5 and fuming sulfuric acid (25 % SO 3 ) in a sealed glass tube at 200 °C led to red, needle shaped single crystals of Re 2 O 4 Cl 4 (SO 4 ) (monoclinic, C 2/ c , a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9)°, Z = 8). In the crystal structure the [ReO 2 ] moieties are linked by [SO 4 ] 2– tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to [ReO 2/1 Cl 2/1 (SO 4 ) 2/4 ].

Description: The new polymorph of sodium tetraborate HP-Na 2 B 4 O 7 was synthesized under high-pressure / high-temperature conditions of 6 GPa and 1000 °C in a multianvil apparatus with a Walker-type module. HP-Na 2 B 4 O 7 crystallizes with nine formula units per cell in the trigonal chiral space groups P 3 2 21 or P 3 1 21 . The parameters are a = 765.5(2), c = 2142.3(4) pm, V = 1.0872(3) nm 3 , R 1 = 0.0581, and wR 2 = 0.0809 (all data). The crystal structure of HP-Na 2 B 4 O 7 is built up from interconnected “sechser” rings of alternating corner-sharing BO 3 and BO 4 groups.

Description: Abstract. By direct reactions of selenium with halogen and trimethylphenylammonium halogenide and tetraphenylphosphonium, ethyltriphenylphosphonium, and methyltriphenylphosphonium bromides, the tetrahalogenidoselenates(II) – bis(trimethylphenylammonium)tetrabromidoselenate(II) bromide, [NPhMe 3 ] 2 [SeBr 4 ] · [NPhMe 3 ]Br, a mixed bis(trimethylphenylammonium) tetra(bromido/chlorido)selenate(II), [NPhMe 3 ] 2 [SeBr 4– x Cl x ] · [NPhMe 3 ] 2 SeBr 1– y Cl y ], [NPhMe 3 ] 2 [SeBr 4– x Cl x ],the haxahalogenidodiselenates(II) – bis(trimethylphenylammonium) hexabromidodiselenate(II), [NPhMe 3 ] 2 [Se 2 Br 6 ], bis(trimethylphenylammonium) hexachloridodiselenate(II), [NPhMe 3 ] 2 [Se 2 Cl 6 ], a mixed bis(trimethylphenylammonium) bromido/chlorido-diselenate(II), [NPhMe 3 ] 2 [Se 2 Br 5 Cl], bis(tetraphenylphosphonium) hexabromidodiselenate(II), [PPh 4 ] 2 [Se 2 Br 6 ], bis(ethyltriphenylphosphonium) hexabromidodiselenate(II), [PEtPh 3 ] 2 [Se 2 Br 6 ], and bis(methyltriphenylphosphonium) hexabromidodiselenate(II), [PMePh 3 ] 2 [Se 2 Br 6 ], were prepared. By the reaction of selenium with bromine in acetonitrile in the presence of trimethylphenylammonium, benzyltrimethylammonium, and tetramethylammonium bromides, the salts of the unique bromidoselenate(I) anions – bis(trimethylphenylammonium) hexabromidotetraselenate(I), [NPhMe 3 ] 2 [Se 4 Br 6 ], bis(benzyltrimethylammonium) hexabromidotetraselenate(I), [NBzMe 3 ] 2 [Se 4 Br 6 ], and bis(tetramethylammonium) octadecabromidohexadecaselenate(I), [NMe 4 ] 2 [Se 16 Br 18 ], were isolated. First mixed-valence bromidoselenates(II/I) – bis(tetraethylammonium) octabromidotriselenate(II){dibromidodiselenate(I)}, [NEt 4 ] 2 [Se 3 Br 8 (Se 2 Br 2 )], bis(tetraphenylphosphonium) hexabromidodiselenate(II)-bis{dibromidodiselenate(I)}, [PPh 4 ] 2 [Se 2 Br 6 (Se 2 Br 2 ) 2 ], and tetrakis(tetramethylammonium) bis{decabromidotetraselenate(II)}-bis{dibromidodiselenate(I)}, [(CH 3 ) 4 N] 4 [(Se 4 Br 10 ) 2 (Se 2 Br 2 ) 2 ] – were synthesized. Mixed bis(trimethylphenylammonium) hexabromidoselenate/tellurate(IV), [NPhMe 3 ] 2 [Se 0.75 Te 0.25 Br 6 ], catena -poly[(di-μ-bromidobis-{tetrabromidoselenate/tellurate(IV)})- μ-bromine], [NPhMe 3 ] 2n [Se 1.5 Te 0.5 Br 10 · Br 2 ] n were isolated. First mixed-valence bromidoselenate(IV/I)-bis(trimethylphenylammonium) hexabromidoselenate(IV)-bis{dibromidodiselenate(I)}, [NPhMe 3 ] 2 [SeBr 6 (Se 2 Br 2 ) 2 ], a number of mixed bromidochalcogenates(IV/I) – bis(trimethylphenylammonium), bis(tetraethylphosphonium), bis(ethyltriphenylphosphonium) hexabromidotellurates(IV)-bis{dibromidodiselenates(I)}, [NPhMe 3 ] 2 [TeBr 6 (Se 2 Br 2 ) 2 ], [PEt 4 ] 2 [TeBr 6 (Se 2 Br 2 ) 2 ], [PEtPh 3 ] 2 [TeBr 6 (Se 2 Br 2 ) 2 ], bis(triethylmethylammonium) hexabromidotellurate(IV)-tris{dibromidodiselenate(I)}, [NMeEt 3 ] 2n [TeBr 6 (Se 2 Br 2 ) 3 ] n , were synthesized. Mixed-valence bromidoselenate(IV/II) – bis(methyltriphenylphosphonium) hexabromidoselenate(IV)-bis{dibromidoselenate(II)},[PMePh 3 ] 2 [SeBr 6 (SeBr 2 ) 2 ], received by direct synthesis and two mixed-valence bromidochalcogenates(IV/II) – bis(methyltriphenylphosphonium) and bis(tetrapropylammonium) hexabromidotellurates(IV)-selenates(II), [PMePh 3 ] 2 [TeBr 6 (SeBr 2 ) 2 ] and [N n Pr 4 ] 2 [TeBr 6 (SeBr 2 ) 2 ], were synthesized from elemental selenium, tellurium dioxide, and corresponding onium bromide. The structures of all compounds were determined by X-ray diffraction.

Description: A straightforward way for the preparation of the energetic 5-aminotetrazolium and 1,5-diaminotetrazolium salts is reported. The energetic salts were readily synthesized by the reaction of 5-aminotetrazolium nitrate or 1,5-diaminotetrazolium nitrate with ammonium 5-nitroiminotetrazolate, ammonium 1-methyl-5-nitroiminotetrazolate, bis(ammonium) ethylene bis(5-nitroiminotetrazolate), and diammonium iminobis(5-tetrazolate), respectively, in water under mild conditions. All products were recovered as highly crystalline materials in excellent yields and purities, and were fully characterized by IR spectroscopy, 1 H and 13 C NMR spectroscopy, DSC measurements as well as elemental analyses.

Description: The cover picture shows a collage of figures from articles in this Special Issue. A diverse collection of emphasizing intermetallic compounds is assembled herein. The contributions range from novel synthetic strategies to obtain new compounds as well as to grow crystals suitable for specific measurements of physical properties, through complex structural problems solved by combinations of diffraction and electronic structure theory, to summarizing some important and novel applications for these materials.

Description: Four binary lanthanum stannides close to the 1:1 ratio of Sn:La were synthesized from mixtures of the elements. The structures of the compounds have been determined by means of single-crystal X-ray data. The low temperature (α) form of LaSn (CrB-type, orthorhombic, space group Cmcm , a = 476.33(6), b = 1191.1(2), c = 440.89(6) pm, Z = 4, R 1 = 0.0247), crystallizes with the CrB-type. The structure exhibits planar tin zigzag chains with a Sn–Sn bond length of 299.1 pm. In contrast to the electron precise Zintl compounds of the alkaline earth elements, additional La–Sn bonding contributions become apparent from the results of band structure calculations. In the somewhat tin-richer region, the new compound La 3 Sn 4 (orthorhombic, space group Cmcm , a = 451.45(4), b = 1190.44(9), c = 1583.8(2) pm, Z = 4, R 1 = 0.0674), crystallizing with the Er 3 Ge 4 structure type, exhibits Sn 3 segments of the zigzag chains of α-LaSn together with a further Sn atom in a square planar Sn coordination with increased Sn–Sn bond lengths. In the Lanthanum-richer region, La 11 Sn 10 (tetragonal, space group I 4/ mmm , a = 1208.98(5), c = 1816.60(9) pm, Z = 4, R 1 = 0.0325) forms the undistorted tetragonal Ho 11 Ge 10 structure type. Its structure, which contains isolated Sn atoms, [Sn 2 ] dumbbells and planar [Sn 4 ] rings is related to the high temperature (β) form of LaSn. The structure of β-LaSn (space group Cmmm , a = 1766.97(6), b = 1768.28(5), c = 1194.32(3) pm, Z = 60, R 1 = 0.0453), which forms a singular structure type, can be derived from that of La 11 Sn 10 by the removal of thin slabs. Due to the different stacking of the remaining layers, planar [Sn 4 ] chain segments and linear [Sn–Sn–Sn] anions are formed as additional structural elements. The chemical bonding (Sn–Sn covalent bonding, Sn–La contributions) is discussed on the basis of the simple Zintl concept and the results of FP-LAPW calculations (density of states, band structure, valence electron densities and electron localization function).

Description: Our work emphasized on synthesizing and characterizing neutral mononuclear copper(II) complexes with second generation fluoroquinolone drug ciprofloxacin (CFL) and some bipyridine derivatives (A n ) of type [Cu(CFL)(A n )Cl] · 2H 2 O. The DNA binding free energies were evaluated by studying the effect of salt concentrations on DNA binding. DNA interactions were investigated by using DNA melting temperature studies, viscosity measurements, absorption titration, and gel electrophoresis experiments. Also superoxide dismutase (SOD)-like activity (IC 50 values) and antibacterial activity of metal complexes were studied. To validate the proper mechanistic pathway for plasmid DNA cleavage, gel electrophoresis experiments were carried out in presence of radical scavenging agents. The bactericidal activity of metal complexes was evaluated in terms of colony forming unit.

Description: Three copper(II) coordination polymers, namely, {[CuL(H 2 O) 2 ] · 4H 2 O} n ( 1 ), [CuL(H 2 O)(DMF)] n ( 2 ), and [CuL(2,2′-bipy)(DMSO)] · DMSO ( 3 ) [H 2 L = 2,2′-(4,6-dinitro-1,3-phenyl-enedioxy)diacetic acid] were synthesized in different solvents (H 2 O, DMF, and DMSO). X-ray single crystal diffraction studies show that both complexes 1 and 3 belong to triclinic crystal system and P 1 space group and complex 2 belongs to the monoclinic crystal system and P 2 1 / c space group. In three complexes, all the central Cu II ions coordinate with the ligand, forming a square pyramidal configuration. Both complexes 1 and 2 show similar 1D chain-like structure and the chains are further connected by hydrogen bonds, forming 3D frameworks. Complex 3 exhibits a 0D structure due to the introduction of the ligand 2,2′-bipy. In addition, the luminescence properties of these complexes were investigated.

Description: The mononuclear amidinate complexes [(η 6 -cymene)-RuCl( 1a )] ( 2 ) and [(η 6 -C 6 H 6 )RuCl( 1b )] ( 3 ), with the trimethylsilyl-ethinylamidinate ligands [Me 3 SiC≡CC(N- c -C 6 H 11 ) 2 ] – ( 1a – ) and[Me 3 SiC≡CC(N- i -C 3 H 7 ) 2 ] – ( 1b – ) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(η 5 -C 5 H 5 )Ru(PPh 3 )( 1b )] ( 4a ) [(η 5 -C 5 Me 5 )Ru(PPh 3 )( 1b )] ( 4b ), and [(η 6 -C 6 H 6 )Ru(PPh 3 )( 1b )](BF 4 ) ( 5 -BF 4 ) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl-silyl group using [Bu 4 N]F resulted in the isolation of [(η 6 -C 6 H 6 )Ru(PPh 3 ){(N- i -C 3 H 7 ) 2 CC≡CH}](BF 4 ) ( 6 -BF 4 ) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a / b to 6 -BF 4 were characterized by multinuclear NMR ( 1 H, 13 C, 31 P) and IR spectroscopy and elemental analyses, including X-ray diffraction analysis of 1b , 2 , and 3 .

Description: The cover picture shows the molecular structure of 1,2-diisopropyl-1,2-diaza-3,5-diphenyl 3,5-diborolidine as well as those of a potassium- and a mercury derivative. The latter compound was obtained by the reaction of the diborolidine with potassium-bis-(trimethylsilyl)-amide and subsequent treatment of the potassium salt with HgCl 2 . Such heterocyclic derivatives are interesting as potential precursors for cyclic diborylcarbene ligands. A new synthetic pathway to this ring system and more details are discussed in the article by Lothar Weber and Jan B. Förster et al. on 1711ff.

Description: Two cobalt complexes, [Co 3 (L) 2 (CH 3 OH) 2 (μ 3 -OH) 2 ] ( 1 ) and [Co(L)(bpe) 0.5 ] · H 2 O ( 2 ) [H 2 L = 5-(4-carboxyphenoxy)-pyridine-2-carboxylic acid; bpe = 1,2-bis(4-pyridyl)ethylene] were synthesized and fully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis (TGA), and magnetic analysis. Complex 1 has a two-dimensional (2D) structure with puckered Co–O–Co chains, and 2 displays a three-dimensional (3D) network containing one-dimensional rectangular channels with dimensions of 9.24 × 13.84 Å. In complex 1 , variable-temperature magnetic susceptibility measurements indicate antiferromagnetic interactions between cobalt magnetic centers.

Description: Single crystals of the phase Yb 3 Co 4– x Ru x Sn 13 ( x = 0, 0.38) were grown by the flux growth method and were characterized by single crystal and powder X-ray diffraction. Magnetic, resistivity, and thermopower measurements were performed on both doped and undoped single crystals of Yb 3 Co 4– x Ru x Sn 13 . The Ru-doped compound shows a sign change of the thermopower at approximately 150 K, indicating both electron and hole conductivity, as well as a complete suppression of the ytterbium magnetic moment exhibited by undopedYb 3 Co 4 Sn 13 . Single crystal X-ray diffraction studies at 100 K, 298 K, and 375 K were performed, and the results are compared to published theoretical models.

Description: Complex metallic phases in the Al–Cr–Fe system are considered to be interesting because of their enhanced resistance against corrosion. Single crystal growth of the Al 4 (Cr,Fe) and Al 13 (Fe,Cr) 4 phases, which is a prerequisite for detailed studies is presented herein for the first time. Along with their binary end members Al 4 Cr and Al 13 Fe 4 growth of cm 3 -size crystals was achieved by using the Czochralski method from Al-rich solutions at temperatures of approximately 1000 °C. Special emphasis is put on the refinement of the Al-rich corner of the ternary phase diagram in determining the 1000 °C equilibria between the incongruent melts and the corresponding ternary solid solutions. Our findings confirm earlier data on the existence region of Al 13 (Fe,Cr) 4 , but significantly differ from those with respect to the so called Al 4 (Cr,Fe) phase. It is shown that the existence region of Al 4 (Cr,Fe) decomposes into four regions of structurally different phases depending on the Cr/Fe ratio. Binary μ-Al 4 Cr crystallizes in the hexagonal space group P 6 3 / mmc and can dissolve only up to about 1 At-% iron. More Fe-rich alloys crystallize in the orthorhombic space group Cmcm (about 2 At-% iron) or Immm (containing between 3 and about 6 At-% iron). For crystals containing about 7 At-% iron the structure belongs to the space group R . The grown single crystals were characterized by electron probe microanalysis revealing only weak segregation effects. The structural perfection of the orthorhombic phase was studied using X-ray topography with the Lang technique. Significant anisotropic properties of this phase allow to discuss structural similarities with decagonal quasicrystals.

Description: The minimal occupancy level ( θ min ) of the clathrate lattice of gas molecules is defined as the number of guest molecules in the host clathrate lattice, which can stabilize the thermodynamically unstable empty cage by covering the energy demand of the transformation of hexagonal ice into empty clathrate lattice (Δ H trans ). The θ min values for chlorine hydrate were determined from the n = f ( p ) T =const . relationship and the average molar intercalation heat of chlorine in the type I clathrate lattice was also calculated for both type of cavities.

Description: The reactivity of cyanuric acid towards alkali triazinetricarboxylates was investigated and the first triazine-triazine adduct phases comprising alkali metal ions were synthesized and characterized by single-crystal X-ray diffraction and thermal analysis. An investigation of the reaction between the alkali triazine tricarboxylates M 3 [C 3 N 3 (CO 2 ) 3 ] · x H 2 O ( M = Li, Na, K, Rb, Cs) and cyanuric acid showed that the degree of ion transfer from triazine tricarboxylate to cyanuric acid increases gradually from the lithium to the cesium salt reflecting an increasing basicity of the triazine tricarboxylates.The reaction of potassium and rubidium triazine tricarboxylate dihydrate with cyanuric yielded the novel co-crystalsK 3 [C 3 N 3 (CO 2 ) 3 ][C 3 N 3 O 3 H 3 ] · H 2 O ( 3a ) and Rb 3 [C 3 N 3 (CO 2 ) 3 ][C 3 N 3 O 3 H 3 ] · H 2 O ( 3b ). In comparison to metal free triazine-triazine adduct phases in these compounds the assembly of molecules in the crystal is mainly determined by Coulomb interactions and only to a certain degree by hydrogen bonds and dispersive interactions. In the crystal the s -triazine units exhibit a layered structure with triazine tricarboxylate and isocyanuric acid being arranged in zigzag strands within the layers and stacked in columns perpendicular to the layers. Thermal analysis revealed a quite weak cohesion between triazine tricarboxylate and cyanuric acid upon heating.

Description: Full structural analysis of Preyssler-type phosphotungstic acid, H 14 [P 5 W 30 O 110 Na], using 183 W NMR, 31 P NMR, and IR spectroscopy, as well as complete elemental analysis revealed that H 14 [P 5 W 30 O 110 Na] · 44H 2 O was obtained in pure form. H 14 [P 5 W 30 O 110 Na] started to decompose by heating at 373 K and was less stable than Keggin-type phosphotungstic acid, H 3 PW 12 O 40 · 6H 2 O, which was stable even after heating at 673 K. Acidic strength measurements using trimethyl phosphine oxide (Me 3 P=O) as a probe molecule indicated that the acidic strength of H 14 [P 5 W 30 O 110 Na] was greater than that of H 3 PW 12 O 40 on the basis of the amount of acid in an aqueous solution. H 14 [P 5 W 30 O 110 Na] was less active than H 3 PW 12 O 40 for hydrolysis of alkyl acetates on the basis of acid amount. However, H 14 [P 5 W 30 O 110 Na] was more active than H 3 PW 12 O 40 for hydrolysis of alkyl acetates with small alkyl groups on the basis of catalyst weight because acid amount per weight of H 14 [P 5 W 30 O 110 Na] was about two times higher than that of H 3 PW 12 O 40 .

Description: New crystalline mercury halide adducts with polyetheras ligands were isolated, characterized, and identified as trans -[Hg II Cl 2 (diox) 2 ] n ( 1 ) and trans -[Hg II I 2 (diox)] n ( 2 ). The compounds were obtained from the metal halide salts in solution of 1,4-dioxane and can be considered as “cutting-out” products from the metal halide as they show similarity in the arrangement with starting compounds.

Description: Li 2 Sr 4 Al 2 Ta 2 N 8 O was synthesized from Li 3 AlN 2 , Sr(NH 2 ) 2 , LiN 3 , and lithium metal as fluxing agent in weld shut tantalum crucibles. Single crystals were obtained as byproduct from reaction with the ampoule material. The crystal structure ( P 2 1 / n (no. 14), a = 9.4081(19), b = 10.012(2), c = 5.9832(12) Å, β = 93.44(3)°, Z = 2) was solved on the basis of single-crystal X-ray diffraction data. Li 2 Sr 4 Al 2 Ta 2 N 8 O is built up of vertex sharing AlN 4 and TaN 4 tetrahedra, forming a BCT-zeolite type structure with Sr 2+ ions and molecular Li 2 O units incorporated into the voids. Lattice energy calculations (MAPLE) confirmed the electrostatic bonding interactions and the chemical composition.

Description: Hydroalumination or hydrogallation of tri(ethynyl)silanes, R Si(C≡C-Ar) 3 ( 1a , R = Ph, Ar = Ph; 1b , R = Me, Ar = Ph; 1c , R = Me, Ar = C 6 H 4 Me), with the element hydrides H- Et Bu 2 ( E = Al, Ga) in stoichiometric ratios of 1:1 to 1:3 at ambient temperature yielded the addition products (PhC≡C) 2 ( R )Si[( t Bu 2 E )C=C(H)Ph] ( 2 , R = Ph, E = Ga; 3a , R = Me, E = Al; 3b , R = Me, E = Ga), (PhC≡C)(Me)Si[( t Bu 2 E )C=C(H)Ph] 2 ( 4a , E = Al, 4b , E = Ga) and (Me)Si[( t Bu 2 Al)C=C(H)Ar] 3 ( 5 , Ar = Ph; 6 , Ar = C 6 H 4 Me). Compounds 2 – 4 show a relatively close interaction between the coordinatively unsaturated aluminium or gallium atoms and one of the C α (≡C) atoms of unreacted alkyne substituents [245 ( E = Al) and 266 pm ( E = Ga)] that stabilises the kinetically favoured cis addition products with E and hydrogen on the same side of the resulting C=C double bonds. In the absence of these stabilising effects the compounds were found to isomerise to the thermodynamically favoured trans isomers.

Description: The quaternary compounds In 2 Bi 3 Se 7 I and InBi 2 Se 4 I have been synthesized via gas phase reactions. They decompose above ca. 400 °C, losing iodine and forming binary compounds. Their crystal structures have been solved and refined using single-crystal X-ray diffraction data (In 2 Bi 3 Se 7 I: space group Pnma , a = 13.6720(2), b = 4.0893(3), c = 16.7070(2) Å; InBi 2 Se 4 I: space group Pnma , a = 26.6039(14), b = 4.1285(2), c = 13.5031(9) Å). Both compounds show structural features related to those found in alkali metal bismuth chalcogenides known for their good thermoelectric properties such as β-K 2 Bi 8 Se 13 . All these structures contain rocksalt-like building blocks as well as CdI 2 -like fragments and loosely bound anions (selenide halides) or cations (alkali metal selenides), respectively, located in rather large cavities which suggests the possibility of phonon scattering by rattling. The electrical resistivity of In 2 Bi 3 Se 7 I and InBi 2 Se 4 I conforms to semiconducting behavior.The total thermal conductivity of sintered pellets of In 2 BiSe 4 I exhibits a maximum of 0.7 W · K –1 · m –1 at 22 K. The rather high electrical resistivity of In 2 Bi 3 Se 7 I and In 2 BiSe 4 I is probably a consequence of the different electronegativities of the constituting elements in combination with the balanced valence states. The related compound BiSeI has a lower electrical resistivity and a higher thermal conductivity featuring a maximum of 10.3 W · K –1 · m –1 at 8.2 K; its Seebeck coefficient (S) amounts to –55 μV · K –1 at 295 K.

Description: Organotin compounds are a recurring motif in organometallic chemistry. The syntheses and characterization of new diorganotin compounds with α-oxoglutaric acid isonicotinyl hydrazone are described, prepared compounds were characterized by elemental analysis, UV/Vis, 1 H, and 13 C NMR spectroscopy, and X-ray diffraction. They both have a distorted pentagonal bipyramidal arrangement, with a heptacoordinated central tin atom. Compound 1 presents a centrosymmetric dinuclear framework. Interestingly, intermolecular O–H ··· N and O–H ··· O hydrogen bonds contribute to the two-dimensional network. Compound 2 is a simple mononuclear compound, which exhibits a rare one-dimensional chain constructed by intermolecular O–H ··· Cl and N–H ··· O hydrogen bonds.

Description: A new thallium(I) coordination polymer, [Tl 2 L · H 2 O] n ( 1 ) [H 2 L = 5-(4-hydroxyphenyl)tetrazole], was synthesized and characterized by IR spectroscopy, elemental analysis, and X-ray crystallography. The single-crystal X-ray diffraction data of compound 1 show the existence of two different Tl I ions with differing coordination numbers. The coordination number of Tl I (1) is four and that of Tl I (2) is two. This coordination polymer was used as a precursor for the preparation of Tl III oxide nanoparticles. Thallium(III) oxide was characterized by powder X-ray diffraction and the morphology of nanoparticles characterized by scanning electron microscope (SEM).

Description: . Tungsten trioxide (WO 3 ) films with novel dandelion-like structures were prepared by spin-coating a sol of WO 3 with CTAB (cetyltrimethyl ammonium bromides) on quartz substrates. The resultant WO 3 films were characterized by X-ray diffraction (XRD), FT-IR spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The wettabilities of the WO 3 films were evaluated by contact angle (CA) measurements. It was found that the WO 3 film exhibited superhydrophilicity under UV light irradiation, whereas after storage in the dark for a certain time, it turned to be superhydrophobic.

Description: The complexes [Cu(L 1 )(H 2 O) 2 ](BF 4 ) 2 · 2H 2 O ( 1 ) [L 1 = 5,16-dimethyl-2,6,13,17-tetraazatricyclo(14,4,0 1.18 ,0 7.12 )docosane] and 0.5[Cu(L 2 )(NO 3 ) 2 ][Cu(L 2 )](NO 3 ) 2 ( 2 ) [L 2 = dibenzyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo(14,4,0 1.18 ,0 7.12 )docosane] were synthesized and characterized by single crystal X-ray analyses. In these constrained macrocycles, the central copper(II) atoms are in a tetragonally distorted octahedral environment with four nitrogen atoms of the macrocyclic ligands in equatorial positions and oxygen atoms from either water molecules or nitrato groups in axial positions. The macrocyclic ligands in both complexes adopt the most stable trans -III conformation. The Cu–N distances [1.999(7)–2.095(7) Å] are typical for such complexes, but the axial ligands are weakly coordinating Cu–OH 2 bonds [2.693(3) Å] and Cu–ONO 2 bonds [2.873(7) Å] due to the combination of the pseudo Jahn–Teller effect and strong in-plane ligand field. The crystals are stabilized by a three-dimensional network by hydrogen bonds that are formed among the secondary nitrogen hydrogen atoms, oxygen atoms of water molecules, fluorine atoms of BF 4 – , and oxygen atoms of NO 3 – . The electronic absorption and IR spectroscopic properties are also discussed.

Description: Zirconium and hafnium were incorporated into the Gd 5 Ge 4 and Gd 5 Si 4 parent compounds in order to study the metal-site occupation in the M 5 X 4 magnetocaloric phases ( M = metals; X = p elements) family. The Gd 5– x Zr x Ge 4 phases adopt the orthorhombic Sm 5 Ge 4 -type (space group Pnma ) structure for x ≤ 1.49 and the tetragonal Zr 5 Si 4 -type ( P 4 1 2 1 2) structure for x ≥ 1.77. The Gd 5 –x Hf x Si 4 compounds crystallize in the orthorhombic Gd 5 Si 4 -type ( Pnma ) structure for x ≤ 0.41 and the Zr 5 Si 4 -type structure for x ≥ 0.7. In both systems, single-crystal X-ray diffraction reveals that the Zr/Hf atoms preferentially occupy the slab-surface M 2 and slab-center M 3 sites, both of which have a significantly larger Zr/Hf population than the slab-surface M 1 site. The metal-site preference, i.e. the coloring problem on the three metal sites, is discussed considering geometric and electronic effects of the local coordination environments. The analysis of the metal-site occupation in Gd 5– x Zr x Ge 4 and Gd 5 –x Hf x Si 4 as well as other metal-substituted M 5 X 4 systems suggests that both geometric and electronic effects can be used to explain the metal-site occupation.

Description: The structure of trans -[Cr(tn) 2 Br 2 ]ClO 4 (tn = propane-1,3-diamine) has been determined by a single-crystal X-ray diffraction study at 100 K. The complex crystallizes in the space group P of the triclinic system with two mononuclear formula units in a cell of dimensions a = 6.8220(4), b = 8.86199(9), c = 12.6644(8) Å and α = 77.859(7)° , β = 81.765(6)°, and γ = 77.764(7)°. The chromium atom is in a slightly distorted octahedral environment coordinated by four nitrogen atoms of two tn ligands and two bromine atoms in trans positions. The two six-membered chelate rings in the complex cations are oriented in an anti chair-chair conformation with respect to each other. The mean Cr–N(tn) and Cr–Br bonds are 2.093(3) and 2.4681(4) Å, respectively. The crystal packing is stabilized by hydrogen bonds. The infrared and electronic absorption spectral properties are consistent with the result of X-ray crystallography. It is confirmed that the nitrogen atoms of the tn ligand are strong σ-donors, but the bromido ligands have weak σ- and π-donor properties toward the chromium(III) ion.

Description: The choice of solvent (alcohol or hydrocarbon), oxidising agent (air, pure oxygen or hydrogen peroxide), and temperature (ambient to boiling solution) is significant in the oxidation of Co(thd) 2 [(thd) – = anion of H(thd) = C 11 H 20 O 2 = 2,2,6,6-tetramethylheptane-3,5-dione]. With EtOH as solvent, refluxing conditions, and oxygen atmosphere the solid reaction product was established as a 2:1 stoichiometric mixture of Co(thd) 3 and Co 3 (thd) 3 (EtO) 4 ( tert -BuCOO). The relative amount of Co(thd) 3 increases somewhat with decreasing reaction temperature. One third of the cobalt atoms in Co 3 (thd) 3 (EtO) 4 ( tert -BuCOO) retain their original Co II state (the rest being oxidised to Co III ). With MeOH as solvent negligible amounts of cobalt are available for oxidation since the Co II state instead becomes tied up in Co 4 (thd) 4 (MeO) 4 (MeOH) 4 which is virtually insoluble in MeOH. Complete oxidation of Co II to Co III occurs in 1- and 2-propanol, but apart from Co(thd) 3 the composition of the poorly crystalline products could not be identified. The crystal and molecular structures of Co 3 (thd) 3 (EtO) 4 ( tert -BuCOO) have been determined by single-crystal X-ray diffraction [ a = 9.811(4), b = 22.528(8), c = 50.516(5) Å, β = 99.178(7)° at 150 K; space group P 2 1 / c ]. The molecular structure comprises a triangular Co 3 central cluster linked together by Co–O–Co bridges. The arrangement in the central cluster can be viewed as a cuboid-resembling Co 3 O 4 configuration (viz. a Co 4 O 4 cuboid with one cobalt vertex vacant). The coordination of the Co III atoms is approximately octahedral whereas that of the penta-coordinated Co II atoms is distorted square pyramidal.

Description: The R 5 T 4 intermetallic compounds of rare earth elements ( R ) with the group 14 elements ( T ) adopt a number of layered crystal structures that reversibly transform into each other. The transformations proceed through massive shear displacements of their main structural units, i.e. slabs, which are pseudo two dimensional blocks of atoms stacked along a certain crystallographic direction. These transformations can be triggered by change in chemical composition of the compounds (including partial substitutions of the group 14 elements by the group 13 or 15 elements), temperature, applied pressure, or applied magnetic field. The physical properties of these compounds are usually intimately related to their crystallography, and especially the concomitant magnetic and crystallographic transitions. As a result, strong magnetocaloric, magnetostrictive, magnetoresistance, and other effects are commonly observed. Consequently, a large change of the materials' properties can be achieved by a relatively weak change of external thermodynamic conditions.

Description: Four new copper chalcogenide clusters with trimethylsiloxy groups in the ligand shell have been synthesized and characterized by single-crystal X-ray diffraction. The compounds [Cu 22 Se 6 (S-C 6 H 4 -OSiMe 3 ) 10 (PPh 3 ) 8 ] ( 1 ), [Cu 36 Se 8 (S-C 6 H 4 -OSiMe 3 ) 20 (PPh 3 ) 8 ] ( 2 ) and [Cu 52 Se 20 (S-C 6 H 4 -OSiMe 3 ) 12 (PPh 3 ) 11 ] ( 3 ) are core-shell -cluster, in which the heavy atom frameworks are built up of a copper selenide core which is partly surrounded by a copper thiolate shell. They were synthesized by the reaction of CuOAc and PPh 3 with p -Me 3 SiS-C 6 H 4 -OSiMe 3 and Se(SiMe 3 ) 2 in different ratios. The arrangements of the chalcogen atoms in 1 and 2 are similar to a close packing, while cluster 3 has a new unusual structural motif. In addition the analogous precursor p -Me 3 SiSe-C 6 H 4 -OSiMe 3 was synthesized and investigated in the cluster synthesis. The reaction with CuOAc, PPh 3 and Se(SiMe 3 ) 2 leads to the formation of the functionalized copper selenide cluster [Cu 22 Se 6 (Se-C 6 H 4 -OSiMe 3 ) 10 (PPh 3 ) 8 ] ( 4 ). This compound is similar to 1 and consists of a Cu 22 Se 16 core instead of a Cu 22 Se 6 S 10 core. The functionalization of the cluster compounds with trimethylsiloxy-groups leads to a high solubility of these cluster.

Description: Thus far, three different ribbons and layers of antimony atoms with various Sb–Sb bonds were found in Hf 5 Sb 9 , HfSb 2 and HfSbTe. We uncovered a new variant when trying to dope Hf 5 Sb 9 with tellurium atoms, namely HfSb 2– x Te x , with 0.4 ≤ x ≤ 0.7. HfSb 2– x Te x adopts the monoclinic OsGe 2 type, space group C 2/ m , a = 10.5216(8) Å, b = 3.7142(3) Å, c = 8.5924(7) Å, β = 11.571(1), V = 292.05(4) Å 3 ( Z = 4) when x = 0.5. This structure is composed of a layer of puckered six-membered rings of antimony atoms, with Sb–Sb distances of 2.82 and 3.12 Å. The different antimony atom substructures are compared in this article. Independent of the exact Sb/Te ratio, monoclinic HfSb 2– x Te x is predicted to be metallic, as are Hf 5 Sb 9 , HfSb 2 and orthorhombic HfSbTe.

Description: The reaction of dipicolinic acid, dipicH 2 , with vanadyl sulfate in the mixture of ethanol and water led to the formation of[VO(dipic)(H 2 O) 2 ] · C 2 H 5 OH ( 1 ) and [VO(dipic)(H 2 O)(OC 2 H 5 )] ( 2 ). Complex 1 was obtained first and complex 2 after prolonged standing of the mother liquor in air. Both complexes were characterized by elemental analyses, IR, Raman and UV/Vis spectroscopic analyses and their structures were determined by X-ray diffraction. The vanadium(IV) ion in 1 and vanadium(V) ion in 2 are both coordinated by the O , N , O′ -tridentate dipicolinate ligand. The octahedral coordination of the vanadium(IV) atom is completed by two water molecules in trans position and by an oxo oxygen atom, whereas the vanadium(V) atom is additionally coordinated by an oxo oxygen atom and a water molecule in trans position and by an ethoxido oxygen atom. A co-crystallized ethanol molecule is also present in the crystal structure of 1 . Molecules of [VO(dipic)(H 2 O) 2 ] and ethanol are linked into a 2D network by the O–H ··· O hydrogen bonds in the structure of 1 . Molecules of 2 are assembled into a 3D structure by the O–H ··· O hydrogen bonds.

Description: A novel inorganic-organic hybrid compound [Cu 2 (TTHA)(bpy) 2 (H 2 O)] 2 · 6H 2 O (TTHA = 1,3,5-triazine-2,4,6- triamine hexaacetic acid; bpy = 2,2′-bipyridine) was synthesized and characterized. The compound crystallizes in the triclinic space group P with cell dimensions of a = 10.4837(14) Å, b = 13.0935(17) Å, c = 16.183(2) Å, α = 93.386(2)°, β = 96.181(2)°, γ = 92.570(2)°, V = 2201.7(5) Å 3 and Z = 1. Single-crystal X-ray analysis shows that the structure is made up by a strictly planar CuO 2 Cu ring with monoatomic bridging carboxylate oxygen atoms and a Cu–Cu distance of 3.458 Å. The 3D supermolecular network is constructed by three kinds of interactions including coordinate covalent bonds, hydrogen bonds, and π–π staking interactions. Thermogravimetric analysis, IR spectrum, and PXRD of the compound are given. The variable-temperature magnetic susceptibility analysis of this compound (2–300 K) shows a weak ferromagnetic magnetic exchange interaction with 2 J = 2.23 cm –1 .

Description: Abstract. Reaction of zinc acetate with four different substituted pyrazoles (3,5-dimethyl pyrazole (3,5-Me 2 PzH), 3,5-di- tert -butyl pyrazole (3,5- t Bu 2 PzH), 3,5-diphenyl pyrazole (3,5-Ph 2 PzH), and 5-methyl-3-phenyl pyrazole (3-Ph-5-Me-PzH)) followed by treatment with( η 6 -benzenecarboxylic acid) chromium tricarbonyl afforded the bimetallic zinc-chromium complexes [Zn{( η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5-Me 2 PzH) 2 ], [Zn{( η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5- t Bu 2 PzH) 2 ], [Zn{( η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5-Ph 2 PzH) 2 ], and [Zn{ η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3-Ph-5-Me-PzH) 2 ]. The corresponding bimetallic cadmium-chromium complexes [Cd{( η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5-Me 2 PzH) 2 ] and [Cd{( η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5- t Bu 2 PzH) 2 ] were obtained by using cadmium acetate as starting material. The pyrazole rings and the carboxylate {( η 6 -C 6 H 5 COO)Cr(CO) 3 } – anion act as monodentate ligand in the zinc complexes, whereas a monodentate and bidentate coordination of the {( η 6 -C 6 H 5 COO)Cr(CO) 3 } – anion is observed in the cadmium complexes.

Description: Magnetic properties of GdCo 3 P 2 and GdCo 5 P 3 are reported. Both compounds are paramagnetic at room temperature. GdCo 3 P 2 undergoes an antiferromagnetic transition due to the ordering of gadolinium magnetic moments at 16 K. The cobalt atoms do not contribute to the magnetism of this compound. The antiferromagnetic transition is shifted to lower temperatures by an applied magnetic field, reaching 12 K at 0.60 T. Such behavior is attributed to spin canting or spin reorientation at higher fields. No such abrupt transition is observed in GdCo 5 P 3 , but the field dependence of magnetization at 1.8 K indicates canted antiferromagnetism. In addition, observation of distinct peaks in the AC magnetic susceptibility at 66 K, 54 K, and 48 K suggests occurrence of successive magnetic state changes. An examination of previously determined crystal structures of these solids reveals common structural elements derived from the [Co 2 P 2 ] layer present in the structure of RE Co 2 P 2 phases ( RE = rare earth; ThCr 2 Si 2 structure type). In GdCo 3 P 2 and GdCo 5 P 3 , such layers are truncated and form triangular patterns when viewed along the [010] crystallographic direction. Single-crystal X-ray diffraction analysis showed that GdCo 5 P 3 is isostructural to YCo 5 P 3 . The gadolinium atoms form chains along [010] with d (Gd–Gd) = 3.683 Å. In GdCo 3 P 2 , the gadolinium atoms form cobalt-centered trigonal prisms with d (Gd–Gd) approx. 3.7–3.8 Å. The prisms share their trigonal faces to form columns along [010].

Description: Five new lanthanide(III) diphosphonates, namely, Ln [(HL)(H 2 O)] · H 2 O [ Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ), Nd ( 4 ), Sm ( 5 ); H 4 L = C 6 H 11 N(CH 2 PO 3 H 2 ) 2 ] were synthesized under hydrothermal reaction conditions at 140 °C and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, IR spectroscopy, elemental, and thermogravimetric analysis. Compounds 1 – 5 are isostructural and exhibit a 2D framework structure. The Ln O 8 polyhedra form 1D zigzag chains along the c axis by edge-sharing, which are further interconnected by CPO 3 tetrahedra through edge- and corner-sharing to form a 2D layer in the ac plane. The cyclohexyl groups of the ligands are orientated toward the interlayer space.

Description: A series of cadmium(II) coordination polymers constructed from 1,3-bis(pyridine-3-carbonyl)imidazolidin-2-thioxo (3-bpit) and 1,3-bis(pyridine-4-carbonyl)imidazolidin-2-thioxo (4-bpit), namely,{[Cd(SCN) 2 (3-bpit) 2 ] · 2(CH 3 OH)} n ( 1 ), {[Cd(NO 3 ) 2 (3-bpit) 2 ] · 2(CH 3 OH)} n ( 2 ), [CdI 2 (4-bpit)] n ( 3 ), and [CdCl 2 (4-bpit) 4 ] n ( 4 ) were prepared and characterized by single-crystal X-ray diffraction. Complexes 1 and 2 display different types of infinite 1D helical chain structures, both of which contain 24-membered metallocyclic rings. Complex 3 is composed of 1D zigzag chains, which further form a 3D supramolecular architecture by weak C–H ··· S and S ··· I interactions. Complex 4 also features a 3D supramolecular network assembled from 2D rhombus-shaped layer through intermolecular hydrogen bonding. These structures indicate that the conformation of the ligand and the diverse anions take important roles in the formation of different frameworks. Thermogravimetric and fluorescent properties over complexes are also discussed.

Description: Reactions of [Bu 4 N][ R BF 3 ] [ R = C n F 2 n +1 CF=CF ( cis , trans ), CF 2 =CF, CF 2 =C(CF 3 ), trans -C 4 H 9 CF=CF, trans -C 6 H 5 CF=CF, C 4 H 9 CH=CH ( cis , trans ), CF 3 C≡C, and C 4 H 9 C≡C] with chlorine, bromine, BrF 3 + Br 2 (as equivalent of “BrF”), and ICl in solution (CH 2 Cl 2 , CHCl 3 , CF 3 CH 2 CF 2 CH 3 ) led to 1,2-addition of halogen and/or replacement of boron by halogen (halodeboration). The reaction of [Bu 4 N][CF 3 C≡CBF 3 ] with less than equimolar amounts of diluted fluorine (5 %) in 1,1,1,3,3-pentafluorobutane (PFB) showed only [Bu 4 N][CF 3 CF 2 CF 2 BF 3 ] as fluorine addition product besides extensive fluorodeboration. Suspensions of the insoluble K[CF 2 =CFBF 3 ] salt reacted with Cl 2 and Br 2 in CH 2 Cl 2 giving preferentially products of halogen addition across the C=C bond. In reactions with ICl iododeboration with formation of CF 2 =CFI occurred besides 1,2-addition with formation of [CF 2 I–CFClBF 3 ] – . The halodeboration reaction of[Bu 4 N][ trans -C 4 H 9 CF=CFBF 3 ] with Br 2 , “BrF”, and ICl, of K[ trans -C 6 H 5 CF=CFBF 3 ] with Br 2 , and of [Bu 4 N][ trans -C 4 F 9 CF=CFBF 3 ] with ICl proceeded stereospecifically.

Description: The alkali 1,3,5-triazine-2,4,6-tricarboxylates Li 3 [C 3 N 3 (CO 2 ) 3 ] · 4H 2 O, Rb 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O and Cs 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O were synthesized by saponification of the respective triethyl ester in aqueous solution. In the crystal structure, the triazine tricarboxylate (TTC) units and metal ions are arranged in layers alternating with layers of crystal water molecules. Within the layers the triazine tricarboxylate entities form either strands in Li 3 [C 3 N 3 (CO 2 ) 3 ] · 4H 2 O or a hexagonal arrangement in Rb 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O and Cs 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O. Perpendicular to the layers, the triazine cores exhibit varying degrees of π–π stacking dependent on the metal ions resulting in the formation of rods in Rb 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O and Cs 3 [C 3 N 3 (CO 2 ) 3 ] · 2H 2 O. Additionally, the thermal behavior of the alkali triazine tricarboxylates was investigated by means of FT-IR spectroscopy, TG and DTA measurements. Differences and similarities regarding structural features and thermal behavior are discussed for the obtained novel alkali triazine tricarboxylates and potassium triazine tricarboxylate dihydrate.

Description: A heptacoordinated mononuclear cobalt(II) complex of tridentate bis( N -ethylbenzimidazol-2-ylmethyl)aniline (Etbba) formulated as [Co(Etbba)(pic) 2 ] · (MeCN) (pic = picrate), was synthesized and characterized by elemental analysis, electric conductivity measurements, as well as IR and UV/Vis spectroscopy. The crystal structure of the cobalt(II) complex was determined by single-crystal X-ray diffraction. The study shows the metal atom in a distorted monocapped octahedral arrangement that comprises two picrate molecules and one Etbba ligand molecule. The DNA-binding properties of the cobalt(II) complex were investigated by electronic absorption and fluorescence spectroscopy, as well as viscosity measurements. The experimental results suggest that the cobalt(II) complex binds to DNA in an intercalating mode. In addition, the complex shows strong scavenging effects for hydroxyl radicals.

Description: The reactions of the new nitrilotriacetic acid N ′, N ′, N ′-tri(salicyloyl)trihydrazide (Ntash) with the corresponding metal salts gave four new complexes [Pb 4 (bshz) 2 ] · 2DMF ( 1 ), [Co 2 (bshz)(C 5 H 5 N) 6 ] · 2ClO 4 · (C 5 H 5 N) · 2H 2 O ( 2 ), [Cu 3 (fshz) 2 (C 5 H 5 N) 2 ] ( 3 ), and [Zn 3 (fshz) 2 (C 5 H 5 N) 3 ] n · 2DMF ( 4 ), in which two multidentate ligands, namely N , N ′-disalicyloylhydrazine (H 4 bshz) and N -formylsalicylhydrazide (H 3 fshz) were generated in situ from Ntash. The structures of these complexes were determined by single-crystal X-ray diffraction analysis. Complex 1 presents a novel tetranuclear lead(II) cluster structure with the four lead(II) cations in “hemidirected” coordination spheres. The neighboring tetranuclear clusters of 1 are connected by DMF molecules through weak Pb–O bonds, forming one-dimensional ribbons. Complexes 2 and 3 show dinuclear and linear trinuclear structures with the corresponding Co III and Cu II ions in distorted octahedral and square-planar coordination environments, respectively. Complex 4 exhibits a one-dimensional zigzag chain structure. The magnetic properties of 3 and the photoluminescent properties of 4 were also investigated.

Description: ZnS hollow microspheres were synthesized by a dl -aspartic acid mediated hydrothermal route. dl -aspartic acid plays an important role as crystal growth soft template, which regulates the release of Zn 2+ ions for the formation of ZnS hollow spheres. The formation of these hollow spheres was mainly attributed to an Ostwald ripening process. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), electron diffraction (ED), UV/Vis spectroscopy (UV), and photoluminescence (PL). The shells of the microspheres were composed of ZnS quantum dots (QDs) with the average size of 2.31 nm. The average microspheres diameter is 0.5–3.5 μm. The shell thickness of the hollow sphere is ≈300 nm. The optical bandgap energy increased significantly compared to the bulk ZnS material due to the strong quantum confinement effect. Two strong emissions at ≈425 nm and ≈472 nm in the photoluminescence (PL) spectrum of ZnS hollow microspheres indicate strong quantum confinement because of the presence of QDs.

Description: The isotypic lithium rare-earth oxonitridosilicates Li Ln 5 Si 4 N 10 O ( Ln = La, Pr) were synthesized at temperatures of 1200 °C in weld shut tantalum ampoules employing liquid lithium as flux. Thereby, a silicate substructure with a low degree of condensation was obtained. LiLa 5 Si 4 N 10 O crystallizes in space group P [ Z = 1, LiLa 5 Si 4 N 10 O: a = 5.7462(11), b = 6.5620(13), c = 8.3732(17) Å, α = 103.54(3), β = 107.77(3), γ = 94.30(3), wR 2 = 0.0405, 1315 data, 96 parameters]. The nitridosilicate substructure consists of loop branched dreier single-chains of vertex sharing SiN 4 tetrahedra. Lattice energy calculations (MAPLE) and EDX measurements confirmed the electrostatic bonding interactions and the chemical compositions. The 7 Li solid-state MAS NMR investigation is reported.