ALBERT

Description: The reactions of As 2 O 3 , SbCl 3 , and (BiO) 2 CO 3 with oleum (65 % SO 3 ) yielded single crystals of As(S 2 O 7 )(HS 2 O 7 ) [monoclinic, P 2 1 / c , Z = 4, a = 16.549(1), b = 6.6743(5), c = 9.9498(6) Å, β = 102.672(8)°, V = 1072.672(8) Å 3 ], Sb 2 (SO 4 ) 2 (S 2 O 7 ) [monoclinic, P 2 1 / n , Z = 4, a = 9.1586(2), b = 6.9981(2), c = 17.7956(4) Å, β = 100.9690(8)°, V = 1119.73(5) Å 3 ], and Bi 2 (S 2 O 7 ) 3 [triclinic, P , Z = 2, a = 6.5734(1), b = 10.1954(2), c = 11.5121(2) Å, α = 90.996(1)°, β = 96.976(1)°, γ = 94.870(1)°, V = 762.75(2) Å 3 ]. As(S 2 O 7 )(HS 2 O 7 ) shows the arsenic atoms in a trigonal pyramidal coordination of the oxygen atoms of one chelating S 2 O 7 2– and one monodentate HS 2 O 7 – group. The distinct As(S 2 O 7 )(HS 2 O 7 ) molecules are connected with each other by hydrogen bonds to form layers. Sb 2 (SO 4 ) 2 (S 2 O 7 ) shows the Sb 3+ cations in a seesaw-type coordination of oxygen atoms from both anions. In Bi 2 (S 2 O 7 ) 3 the Bi 3+ cations are in a square prismatic oxygen coordination of disulfate units. The antimony and the bismuth compounds exhibit complex three-dimensionally linked structures. The syntheses and the crystal structures, as well as the thermal decomposition of Sb 2 (SO 4 ) 2 (S 2 O 7 ) are presented.

Description: Silver acetate AgOAc reacts with dry liquid ammonia under the formation of colorless needle-shaped crystals of diammine silver(I) acetate [Ag(NH 3 ) 2 ]OAc ( 1 ). The compound crystallizes in the monoclinic space group P 2 1 / c with a = 8.0205(2), b = 12.4161(3), c = 6.0938(2) Å, β = 107.741(4)°, and V = 577.98(3) Å 3 at 123 K with Z = 4. The crystal structure shows the presence of almost linear [Ag(NH 3 ) 2 ] + cations, which are arranged in a corrugated chain of equidistant silver atoms. The Ag–Ag distance is 3.1089(11) Å, which falls in the range of “argentophilic” interactions. After warming to room temperature and removal of the solvent, compound 1 was found unchanged as evidenced by powder X-ray diffraction, thermogravimetric and mass-spectrometric analysis, as well as IR and Raman spectroscopy.

Description: A series of chalcogenidoantimonates, namely [Zn(NH 3 ) 6 ](Sb III 4 S 7 ) ( 1 ), [Zn(NH 3 ) 6 ]{Zn(NH 3 ) 3 Sb V S 4 } 2 · NH 3 ( 2 ), [Mn(NH 3 ) 6 ](Sb III Se 2 ) 2 ( 3 ) and [Zn(NH 3 ) 4 ]{Zn(NH 3 )Sb III Se 3 } 2 · 3NH 3 ( 4 ) are synthesized by solvothermal technique in liquid ammonia at 50 °C from elemental zinc or manganese, antimony and sulfur or selenium. 1 (space group P ) and 2 ( P ) crystallize centrosymmetrically, whereas 3 ( Pna 2 1 ) and 4 ( P 2 1 ) represent polar structures. All compounds contain discrete cationic [Zn(NH 3 ) 4 ] 2+ , [Zn(NH 3 ) 6 ] 2+ , and [Mn(NH 3 ) 6 ] 2+ ammine complexes. In the anionic structure parts, corner-connected trigonal-pyramidal SbS 3 and SbSe 3 are the characteristic building units. 1 and 4 contain 2D polymeric anions, in the latter case with Zn 2+ cations incorporated in a selenidoantimonate(III) network. The polymeric anion in the structure of 3 is a helical chain. 2 is a molecular compound and contains dinuclear anions [S 3 Sb–S–Zn(NH 3 ) 3 ] 2– with Sb V . Raman measurements show the Sb–Ch valence vibrations in the expected region between 250–370 cm –1 for 1 and at 212 cm –1 for 4 . According to the reflectance spectrum 4 is a semiconductor with an optical band gap of 2.05(5) eV.

Description: . Sr 2 CoOsO 6 , a new osmium based ordered semiconductor double perovskite was prepared by solid state synthesis from the respective binary oxides. Room temperature PXRD analysis shows the compound to be tetragonal [ I 4/ m ; a = 5.5503(1) Å and c = 7.9320(1) Å], whereas low temperature synchrotron data refinement has revealed a second monoclinic polymorph [ I 2/ m ; a = 5.4969(2) Å, b = 5.4979(2) Å, c = 8.0090(1) Å and γ = 90.527(1)°] with a fully ordered rocksalt arrangement of cobalt and osmium atoms over the perovskite B -sites. Heat capacity and magnetic measurements indicate that Sr 2 CoOsO 6 shows antiferromagnetic ordering below T N = 108 K followed by a second magnetic transition at T 2 = 65 K. It was shown that the change from the tetragonal to the monoclinic phase occurs at T N .

Description: . The ternary germanides RE Rh 6 Ge 4 ( RE = Y, La, Pr, Nd, Sm–Lu) were obtained by arc-melting of the elements and subsequent annealing. Single crystals were grown from bismuth fluxes. The samples were studied by X-ray diffraction on powders. The structures of five members were refined from single crystal diffraction data: LiCo 6 P 4 type, P m 2, a = 715.8(1), c = 387.33(8) pm, wR = 0.0238, 332 F 2 values for LaRh 6 Ge 4 , a = 715.0(1), c = 384.96(7) pm, wR = 0.0211, 329 F 2 values for PrRh 6 Ge 4 , a = 714.28(9), c = 382.57(6) pm, wR = 0.0136, 327 F 2 values for SmRh 6 Ge 4 , a = 714.2(1), c = 381.6(1), wR = 0.0270, 327 F 2 values for GdRh 6 Ge 4 , and a = 714.2(2), c = 379.0(1) pm, wR = 0.0273, 324 F 2 values for HoRh 6 Ge 4 with 19 variables per refinement. The RE Rh 6 Ge 4 structures have two crystallographically independent germanium sites in trigonal prismatic coordination, manifesting the close structural relationship with metal-rich phosphides. Together, the rhodium and germanium atoms build up three-dimensional [Rh 6 Ge 4 ] networks, which leave large channels for the rare earth atoms. Each rare earth atom has coordination number 20 with 12 Rh, 6 Ge, and 2 RE neighbors. Temperature dependent magnetic susceptibility measurements indicate Pauli paramagnetic behavior for YRh 6 Ge 4 , LaRh 6 Ge 4 , and LuRh 6 Ge 4 . The compounds RE Rh 6 Ge 4 ( RE = Gd–Yb) are Curie-Weiss paramagnets. Antiferromagnetic ordering was observed at 8.4(5) K (GdRh 6 Ge 4 ), 13.6(5) K (TbRh 6 Ge 4 ), 5.1(5) K (DyRh 6 Ge 4 ), and 8.9(5) K (YbRh 6 Ge 4 ). DyRh 6 Ge 4 and YbRh 6 Ge 4 show metamagnetic transitions at 2.5(5) and 45(2) kOe, respectively.

Description: Reaction of manganese(II) thiocyanate with 2-chloropyrazine leads always to the formation of a compound of composition Mn(NCS) 2 (2-chloropyrazine) 4 ( 1 - Mn/Cl ) that consists of discrete complexes, in which the manganese cation is coordinated by two terminal thiocyanato anions and four 2-chloropyrazine ligands. In contrast, with 2-methylpyrazine only an aqua complex of composition Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 ( 1 - Mn/CH 3 ) is obtained that also consists of discrete octahedrally coordinated complexes. Moreover, a few single crystals of Mn(NCS) 2 (2-chloropyrazine) 4 · Mn(NCS) 2 (2-chloropyrazine) 2 (H 2 O) 2 · 2-chloropyrazine trisolvate ( 2 - Mn/Cl ) and Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 · Mn(NCS) 2 (H 2 O) 4 ( 2 - Mn/CH 3 ) were accidently obtained but no larger amounts are available. On heating, 1 - Mn/Cl and 1 - Mn/CH 3 transforms into new compounds of composition Mn(NCS) 2 (L) 2 (L = 2-chloropyrazine) ( 4 - Mn/Cl ) and 2-methylpyrazine ( 3 - Mn/CH 3 ). Surprisingly on further heating 1 - Mn/CH 3 looses additional 2-methylpyrazine ligands and transforms into a new compound of composition Mn(NCS) 2 (2-methylpyrazine) ( 4 - Mn/CH 3 ). Compound 4 - Mn/Cl is isotypic to its cobalt(II) analog and 4 - Mn/CH 3 is isotypic to Cd(NCS) 2 (2-methylpyrazine) reported recently and therefore, both structures were refined by the Rietveld method. The crystal structures of both compounds are strongly related. They consists of dimeric units, in which each two manganese cations are linked by pairs of μ-1,3-bridging thiocyanato anions, which are further connected into layers by single μ-1, 3-bridging anionic ligands. In contrast to 4 - Mn/Cl , in 4 - Mn/CH 3 these layers are further linked into a 3D coordination network by the 2-methylpyrazine ligands. Magnetic measurements reveal that 1 - Mn/Cl , 1 - Mn/CH 3 , and 3 - Mn/CH 3 shows only Curie- or Curie-Weiss paramagnetism, whereas 4 - Mn/Cl and 4 - Mn/CH 3 shows antiferromagnetic ordering at T N = 22.9 K and at 26.5 K. The results of these investigations are compared with those obtained for related compounds.

Description: . Black platelets of Bi 39.67(7) Ru 2 Br 35.0(2) were crystallized from a melt of Bi, BiBr 3 , and Ru. In the tetragonal crystal structure [ P 4/ mbm , a = 1311.92(6) pm, c = 3018.2(4) pm at 155(5) K], cluster cations [(Bi 8 2+ )Ru 2+ (Bi 8 2+ )] are embedded in a matrix of disordered bromido-bismuthate(III) groups. A thorough analysis of the disorder in the anionic part enabled the unambiguous assignment of the cluster charge. The η 4 -coordination of the two Bi 8 2+ square antiprisms to the Ru II atom in the sandwich complex resembles the bonding of Bi 5 + and Bi 8 2+ in the clusters [(Bi 5 + )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] and [(Bi 8 2+ )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] as well as of Bi 4 2– in 1 ∞ [(Bi 4 2– )Ru + (Bi 4 Br 4 )Ru + ]. By combining crystal chemical considerations for all mentioned compounds and using quantum chemical calculations, a common bonding scheme for the coordination compounds of bismuth polycations and polyanions was established. The η 4 -coordinating bismuth polycations and polyanions act as six electron donors, comparable to nido -carborane ligands, Zintl anions E 9 4– and E 5 6– ( E = Si to Pb), cyclopentadienyl ligands, or the cyclobutadiene dianion. The electron count for the transition metal is 18 in all finite clusters.

Description: . Previous attempts to synthesize and isolate (thiobisphenolate) vanadium(V) dioxido complexes had always provided their dimers containing [O=V(μ-O) 2 V=O] 2+ cores, and these also dominate the solution reactivity. Hence, the behavior of their parent monomers, which represent the major species in solution, has remained uncertain. Herein we report the development of a synthetic route that allowed for the successful isolation, spectroscopic investigation, and structural characterization of the monomer PPh 4 [ S LVO 2 ] ( 3 ) [ S L 2– = 2′2-thiobis(2, 4-di- tert -butylphenolate)]. For this purpose PPh 4 [ S LVOCl 2 ] ( 1 ) had to be accessed first in order to convert it to the ethoxido compound PPh 4 [ S LVO(OEt) 2 ] ( 2 ), which is more prone to hydrolysis. Treatment of 2 with stoichiometric amounts of water followed by immediate cooling to –30 °C led to crystals of 3 . After its dissolution NMR spectra were recorded that were identical with those obtained after dissolution of its dimer, thus confirming the monomer/dimer equilibrium postulated previously. The molecular structure of 3 revealed the absence of a V ··· S interaction, which, however, stabilizes its dimer, and thus suggested the employment of a bisphenolate ligand lacking a bridging sulfur atom to obtain an analogue, which does not undergo dimerization in solution. In Et L 2– the sulfur atom is replaced by an ethylmethine unit and indeed the corresponding complex NBu 4 [ Et LVO 2 ] ( 4 ) proved to be stable as a monomer. Investigation of its potential as a catalyst for the oxidative dehydrogenation of 9-fluorenol confirmed a much lower reactivity in comparison to dimeric complexes, which is discussed.

Description: Two complexes, cis -[MnL 2 (NCS) 2 ] ( 1 ) and cis -[ZnL 2 (NCS) 2 ] ( 2 ) with asymmetrical substituted triazole ligands [L = 3, 4-dimethyl-5-(2-pyridyl)-1, 2, 4-triazole], were synthesized and characterized by elemental analysis, UV/Vis and FT-IR spectroscopy as well as thermogravimetric analyses (TGA), powder XRD, and single-crystal X-ray diffraction. In the complexes, each L molecule adopts a chelating bidentate mode by the nitrogen atoms of pyridyl and triazole. Both complexes have a similar distorted octahedral [ M N 6 ] core ( M = Mn 2+ and Zn 2+ ) with two NCS – ions in the cis position.

Description: . The multi-shaped amorphous alloy (Ni-B) powders were prepared by complexing reduction route using sodium borohydride (NaBH 4 ) as reductant with assistance of ultrasonic wave. The selected complexants, i.e. water, ammonia, salicylic acid, and ethylene diamine tetraacetic acid (EDTA) possess sequentially escalating complexation ability. The chemical composition and shapes of the product samples obtained under different conditions were characterized by X-ray powder differaction, selected area electron diffraction, and transmission electron microscope. The influence of reaction conditions such as the types of Ni-B, temperatures, NaBH 4 concentrations, and sodium hydroxide (NaOH) content on the hydrogen generation rate of hydrolysis of NaBH 4 solution were investigated in detail. The results show that the as-prepared Ni-B powders all belong to amorphous alloy with variable element contents, and the Ni-B sample prepared from EDTA complexation, possessing the best fineness and dispersity, has the strongest catalytic activity. The mean apparent activation energy of the hydrolysis reaction is 64.90 kJ · mol –1 . The NaBH 4 concentration has little impact on hydrogen generation rate, implying that the catalytic hydrolysis of NaBH 4 solution should be the pseudo zero-order reaction. Keeping the NaOH content at below 5 % could inhibit the hydrolysis of NaBH 4 solution, but the NaOH contents from 10 % to 15 % will significantly promote the hydrolysis rate of NaBH 4 . The hydrolysis reaction mechanisms, especially the effect of NaOH content on the hydrolysis reaction were also analyzed.

Description: The intermetallic compounds Sr 2 Au 6.52 Zn 2.48 , Sr 2 Au 6 Zn 3 , and Sr 2 Au 6 Ga 3 were obtained by induction melting of the elements in sealed tantalum tubes. Their structures were studied by X-ray diffraction on powders and refined from single crystal diffraction data: R c , a = 844.5(2), c = 2187.7(5) pm, wR 2 = 0.0411, 936 F 2 values and 20 variables for Sr 2 Au 6.52 Zn 2.48 ; a = 841.6(2), c = 2191.5(7) pm, wR 2 = 0.0126, 587 F 2 values and 19 variables for Sr 2 Au 6 Zn 3 ; and a = 841.9(2), c = 2191.1(7) pm, wR 2 = 0.0199, 660 F 2 values and 19 variables for Sr 2 Au 6 Ga 3 . The gold substructures of Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 can be considered as diamond polytypes with 6R stacking sequences (287–304 pm Au–Au in Sr 2 Au 6 Zn 3 ). The cavities formed by this network are filled in an ordered manner by strontium atoms and Zn 3 (281 pm Zn–Zn), respectively Ga 3 (286 pm Ga–Ga) triangles in a 2:1 ratio. Consequently one can describe the Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 structures as ordered substitution variants of the Zintl phase CaIn 2 . This structural relationship is discussed on the basis of a group-subgroup Scheme. Sr 2 Au 6.52 Zn 2.48 shows Zn/Au mixing on the triangle.

Description: The templated borate, [C 9 H 14 N] · [B 5 O 6 (OH) 4 ], was synthesized under hydrothermal conditions. Single crystal X-ray diffraction techonology reveals that it crystallizes in the triclinic system, space group P (No. 2). The material was also characterized by element analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG-DTA), and luminescence spectroscopy. The compound consisted of isolated pentaborate [B 5 O 6 (OH) 4 ] – and N -butylpyridinium cations [C 9 H 14 N] + . The [B 5 O 6 (OH) 4 ] – anions are connected together by hydrogen bonds to form a three-dimensional framework, in which [C 9 H 14 N] + cations are located in. [C 9 H 14 N] · [B 5 O 6 (OH) 4 ] exhibits tunable luminescence emission at 415–458 nm by means of heating treatment from 100 to 300 °C.

Description: Two alkylimido derivatives of hexamolybdate, (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 3 C 6 H 4 )] ( 1 ) and (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 2 CH 3 C 6 H 4 )] ( 2 ), were synthesized in high purity and good yields by the reaction of [(C 4 H 9 ) 4 N] 4 [α-Mo 8 O 26 ] and methyl anthranilate or ethyl- o -aminobenzoate hydrochloride with N , N ′-dicyclohexylcarbodiimide (DCC) as a dehydrating agent in dry acetonitrile solution, which were characterized by elemental analyses, IR, UV/Vis, and 1 H NMR spectroscopy as well as ESI-MS, and single-crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group P 2 1 / n with one-dimensional chain structure via intramolecular hydrogen bond. Compound 2 also crystallizes in the monoclinic space group P 2 1 / n with dimer structure by intramolecular hydrogen bonds and π–π interactions between the pairs of cluster anions.

Description: The cover picture shows the frontispieces of all articles published in this Special Issue with research reports from DFG priority program 1178 “Experimental Electron Density as Key to Understanding Chemical Interactions”, highlighting the diverse range of chemistry that is covered herein. Biological processes that determine the effects of drugs consist on a certain interaction between agent and receptor. This molecular recognition is influenced by the electron density distribution. Analysis of these processes enables the rational synthesis of drugs. Electron density measurements are moreover significant for the design of advanced materials with specific features, e.g. the development of new pigments. Thus, color, stability, and durability can be tuned by modifying the electron density. Selected substance classes used in chemical synthesis, drug design and material science were analyzed and their binding and recognition processes were studied and quantified by means of electron density measurements.

Description: . Reactions of the coordinatively unsaturated complexes [Fe 2 (μ-P R 2 )(μ-P R ′ 2 )(CO) 5 ] [ R = R ′ = t Bu ( 1 ); R = t Bu, R ′ = Cy ( 2 )] with nitric oxide in toluene at elevated temperatures were investigated. Thus, the new complexes [Fe 2 (μ-P t Bu 2 ) 2 (NO) 4 ] ( 3 ) and [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(NO) 4 ] ( 4 ) were obtained in good yields. The molecular structure of 3 was confirmed by X-ray diffraction study. Compound 4 was also prepared from the coordinatively saturated species [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(CO) 6 ] ( 2a ) with nitric oxide in refluxing toluene. Further closely related reactions at 60 °C with the complex 1 and [FeRu(μ-P t Bu 2 ) 2 (CO) 5 ] ( 5 ), respectively, were investigated using preliminary crystal structure determination results.

Description: Two new materials of the composition ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CoBr 4 ] 2– ( 1 ) and ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2– ( 2 and 3 ), of which the latter exists in two polymorphs, were synthesized. The materials display the synthetically targeted structures, comprising of layers of complex metal ions and layers of long-chain sulfonium cations. The crystal structures of the materials were determined. The interlayer distances are around 24 Å, with metal–metal distances about 8 Å. The magnetic properties of 1 were investigated, and the material is paramagnetic. ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2 is polymorphic. Both polymorphs crystallize with triclinic symmetry.

Description: Single crystals of Rb 2 H 2 P 2 O 6 · 2H 2 O could be obtained from aqueous solutions of hypodiphosphoric acid and rubidium carbonate. Its crystal structure was determined by X-ray diffraction and it crystallizes in the monoclinic space group P 2 1 / c with Z = 4. The salt-like title compound consists of [H 2 P 2 O 6 ] 2– units in staggered P 2 O 6 -skeleton conformation, Rb + cations, and H 2 O molecules, held together by intermolecular hydrogen bonds of the type O ··· O. The vibrational spectra (IR/FIR and Raman) of the rubidium salt were recorded and an assignment of the vibrational modes is proposed based on the point group C 2 h for the P 2 O 6 -skeleton of the anion. The thermal behavior of Rb 2 H 2 P 2 O 6 · 2H 2 O is dominated by a complex TG decay indicating a simultaneous H 2 O delivery coupled with a disproportionation of [H 2 P 2 O 6 ] 2– , what is also supported by Raman spectra of heated samples.

Description: Three metal coordination polymers {[Co(L) 2 (H 2 O) 2 ] 2+ · 2NO 3 – } n ( 1 ), {[Mn(L) 2 (H 2 O) 2 ] 2+ · 2Cl – · 3H 2 O} n ( 2 ), and [ZnL(ba) 2 ] n ( 3 ) [L = 3, 5-bis(imidazole-1-yl)pyridine and Hba = benzoic acid] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and X-ray single crystal diffraction. Complex 1 shows a one-dimensional (1D) chain structure. Adjacent chains are connected by hydrogen bonding and nitrate groups to form a 3D network. Complex 2 features a 2D layer structure. A three-dimensional network is constructed through the cluster consisting of two chloride ions and three water molecules. Complex 3 shows a 1D zigzag chain structure that further twists together to form a 3D network. The X-ray powder diffraction patterns were compared with the simulated ones. Moreover, the luminescent properties of 1 – 3 were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the three complexes.

Description: . The reactions of FeCl 3 · 6H 2 O and 2-(2′-hydroxyphenyl)-2-thiazoline as a bidentate O-N donor thiazoline ligand (thoz) afford a five-coordinate Fe III complex [Fe(thoz) 2 Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz) 2 Cl] was isolated as air-stable crystalline solids and fully characterized, including by single-crystal X-ray structure analysis. Complex [Fe(thoz) 2 Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air.

Description: Two copper(I) complexes of compositions [Cu(HL)I] 2 · EtOH ( 1 ) and [Cu(HL) 3 ]I · MeOH ( 2 ) were synthesized via the reactions of HL [HL = 2(4, 5-diphenyl-1 H -imidazol-2-yl)pyridine] and CuI in EtOH and MeOH, respectively, under solvothermal conditions. The complexes were characterized by X-ray single crystal diffraction, IR spectroscopy, and elemental analysis. Compounds 1 and 2 are catalytically active towards ketalization reaction, giving various ketals under mild conditions.

Description: Mineral samples from the Prasolovskoe epithermal Au-Ag deposit, Russia, were investigated via transmission electron microscopy (TEM). One component was identified as the mineral kurilite Ag 8 Te 3 Se according to the data obtained from electron diffraction (ED) and Fourier transform analyses of high resolution micrographs. Micrometer-sized grains of kurilite were found next to other noble metal chalcogenide domains like the hessite-type. The EDX microprobe analyses of the kurilite domains were determined with the chemical composition Ag 7.9 Au 0.1 Te 2.9 Se 1.0 which is consistent with kurilite doped by gold. Additionally noble metal polychalcogenidehalides (NMPH) were identified via ED. Monoclinic and tetragonal polymorphs of Ag 5 Te 2 Cl were observed for the first time in a mineral sample. One additional component, whose composition equates the kurilite-type component with regard to Ag, Au, Te, and Se but with a marginal chlorine component, crystallizes in a structure type known from synthetic NMPH, namely Ag 23 Te 12 X (X = Cl, Br). This phase as well as the phases Ag 10 Te 4 Br 3 and Ag 20 Te 10 Br 2 was found next to each other in an also investigated synthetic sample.

Description: Eight chelating resins were synthesized in high yields by supporting 2-aminomethylpyridine, 2, 2′-dipyridylamine, 1, 2-phenylenediamine and 1, 2-ethylenediamine on Merrifield and Wang resins, respectively. These resins were used both as support of reducing complexes and as alkali metal sensors. 16 stable and easy to prepare reducing complexes, derived from the chelating resins and LiBH 4 and NaBH 4 , were prepared in good yields. These complexes showed chemoselectivity to reduce aldehydes in a low molar ratio and short time reactions. The fluorescence-sensing behavior of the chelating resins for alkali metal was studied. The fluorescence response of the materials where 1, 2-phenylenediamine is supported on Merrifield and Wang resins indicate that they behave as sensors for Li + and K + , respectively.

Description: The reaction of Fe 3 (CO) 12 with (C 3 H 5 ) 2 NCS 2 K in THF at room temperature afforded a red-brown solution. Treatment of the thus-obtained solution with MeI and PhCH 2 Br afforded clusters 1 , (μ-MeS)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ), and 2 , (μ-PhCH 2 CO)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ). Their structures were unambiguously determined by X-ray crystallography. Therefore, this methodology provides a novel route for the syntheses of spiro-S Fe/S clusters with aminocarbyne ligands.

Description: This study presents the preparation of 5-azido-3-nitro-1 H -1,2,4-triazole ( 1 ) in both good yield and high purity, starting from commercially available chemicals in a three step synthesis. Furthermore, several metal and nitrogen-rich salts with sodium ( 3 ), potassium ( 4 ), cesium ( 5 ), silver ( 6 ), lead ( 7 ), ammonium ( 8 ), guanidinium ( 9 ), and aminoguanidinium ( 10 ) were prepared by simple acid-base reactions. All compounds were well characterized by various means, including vibrational (IR, Raman) and multinuclear ( 1 H, 13 C, 14 N, 15 N) NMR spectroscopy, mass spectrometry, and DSC. Additionally the structure of 7 was determined by single-crystal X-ray diffraction. The sensitivities towards various outer stimuli (impact, friction, electrostatic discharge) were determined according to BAM standards. The metal salts were tested as potential primary explosives utilizing various preliminary tests.

Description: With Sharpless' and Meldal's discovery of the immensely supportive effect that metal catalysis has on Huisgen's classical 1,3-dipolar cycloaddition, azides (RN 3 ) – long underappreciated in organic synthesis – suddenly got in the focus of attention as most crucial players in sensational ‘click chemistry'. Less noisy though with the same commitment and even a much broader scope of scientific topics and objectives, the inorganic azide chemistry has made just as great strides in the last few decades. This review (Part I) gives an introductory survey of the most important results, and informs about modern developments and general trends. Particular emphasis is placed on the recent successful approaches to highly unstable homoleptic azido metal complexes of the main group and early transition elements, as well as on the enormous structural versatility caused by the ‘flexidentate' N 3 – ligand with its unsurpassed bridging capacities. The presentation in this paper of selected compounds and reactions is meant, in a way, as a prelude to the [3+2]-cycloadditions of metal azides and related species which will be covered in-depths in Part II. A large part of the comments finally deals with applications in fields such as catalysis, high explosive performance or magnetism of metal compounds containing azide, today certainly one of the most attractive research areas world-wide.

Description: The long-chain ligand, 1-phenyl-3-methyl-4-heptanoyl-pyrazol-5-one (HL) and its zinc(II) complex ZnL 2 were synthesized. The structure and the properties of ZnL 2 were characterized by elemental analysis, IR spectroscopy, X-ray diffraction, and thermogravimetric analysis. The zinc ion is five-coordinated in a square-pyramidal environment by four oxygen atoms of the HL ligands in the equatorial plane and one water molecule in the axial position. The water molecule is directly bonded to Zn 2+ and involved in intermolecular hydrogen bonding network. The complex and its corresponding ligand were screened in vitro against some strains of the human pathogenic bacteria. The metal complex exhibits higher antibacterial activity than its corresponding ligand. The complex exhibits purple effect emission as the result of fluorescence from the intraligand emission excited state.

Description: The microporous metal-organic framework Cd 2 (ABTC)(H 2 O)(DMA) 2 · H 2 O · 3DMA ( 1 ) (H 4 ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N , N ′-dimethylacetamide) was prepared by solvothermal reaction and characterized. X-ray structure analysis revealed that compound 1 is a three-dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4-connected rectangular ABTC 4– units with 4-connected tetrahedral dinuclear Cd 2 (CO 2 ) 4 (H 2 O)(DMA) 2 secondary building units (SBUs). The solid-state excitation-emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.

Description: P(2-SHC 6 H 4 ) 3 ( PS 3 H 3 ) reacts with GaMe 3 (1:1) to give GaMe{P(2-SC 6 H 4 ) 2 (2-SHC 6 H 4 )-κ 3 S , S′,P } ( 1 ), which could be deprotonated with NEt 3 to give [NEt 3 H][GaMe{P(2-SC 6 H 4 ) 3 -κ 3 S , S′,P }] ( 2 ). The 1:2 reaction of E (2-SHC 6 H 4 ) 3 [ E = P ( PS 3 H 3 ), As ( AsS 3 H 3 )] with GaMe 3 gave the dinuclear complexes GaMe{ E (2-SC 6 H 4 ) 2 (2-S{GaMe 2 (THF)}C 6 H 4 )-κ 3 S , S′,E } [ E = P ( 3 ), As ( 4 )]. Serendipitous hydrolysis of 4 resulted in small amounts of the hexanuclear gallium hydroxide complex cyclo -{GaMe(μ-OH)} 6 {As(2-SC 6 H 4 ) 3 -κ S , S′,S′′ } 2 ( 5 ). Complexes 1 – 4 were fully characterized, complexes 2 – 5 also by X-ray crystallography.

Description: Topological aspects of the experimental electron density in TiB 2 reconstructed on base of the multipole model are obtained from high-resolution single-crystal X-ray diffraction data. The features of electron density are compared with quantum chemical calculations and analysed in terms of Quantum Theory of Atoms in Molecules for the interpretation of atomic interactions. In spite of some differences in the Laplacian, both experimental and calculated density confirmed two main bonding interactions. The B–B bond critical point suggests a shared-type interaction with pronounced ellipticity in the boron layer, whereas B–Ti bond critical point reveals an interaction intermediate between shared and closed-shell type. Both, theory and experiment indicate a non-structured spherical topology in the penultimate shell of Ti. Integration of the electron density over the atomic basins reveals a charge transfer of 1.1 e (experiment) and 1.4 e (theory) from titanium to boron network, respectively.

Description: The stannides Li 2 CuSn 2 and Li 2 AgSn 2 were synthesized by induction-melting (or in a muffle furnace) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of both stannides were investigated by X-ray diffraction on single crystals: Li 2 AuSn 2 type, I 4 1 / amd , a = 442.6(1), c = 1940.9(8) pm, wR 2 = 0.0742, 310 F 2 values for Li 2 CuSn 2 and a = 456.33(9) c = 2018.2(6) pm, wR 2 = 0.0626, 339 F 2 values for Li 2 AgSn 2 with 10 variables for each refinement. The transition metal ( T ) atoms have tetrahedral tin coordination. The T Sn 4 tetrahedra are condensed via common corners forming layers that are further condensed by Sn–Sn bonding, leading to three-dimensional [CuSn 2 ] and [AgSn 2 ] networks which leave distorted hexagonal channels for the lithium atoms. The lithium ions show considerable mobility, with activation energies of 0.29 and 0.47 eV extracted from variable temperature 7 Li solid state NMR spectra. 119 Sn Mössbauer spectra at 78 K show signals at isomer shifts of δ = 2.13(1) mm s –1 for Li 2 CuSn 2 and δ = 2.07(1) mm s –1 for Li 2 AgSn 2 . The signals show electric quadrupolar splitting because of the non spherical environment of the tin nuclei. A minor impurity of β-Sn could be identified in both spectra.

Description: The complexes [Ni 2 (L) 2 ] 2 · H 2 O ( 1 ) and [Cu 2 (L) 2 (H 2 O)] · 2CH 3 OH ( 2 ) were prepared by reaction of the chiral Schiff base ligand N -[(1 R ,2 S )-2-hydroxy-1, 2-diphenyl]-acetylacetonimine (H 2 L) with Ni II and Cu II ions, respectively, aiming to develop economically and environmentally-friendly catalysts for the hydrogenation of ketones. They have a dinuclear skeleton with axial vacant sites. The catalytic effects of the two complexes for hydrogenation of ketones were tested using dihydrogen gas as hydrogen source. They present some catalytic effects in hydrogenation of acetophenone, which has a dependence on the temperature and base used in these reactions. However, no apparent catalytic effects were found for the two complexes in hydrogenation of 4-nitroacetophenone and 4-methylacetophenone. Although the catalytic conversion in these hydrogenation reactions is low, they do represent a kind of cheap and environmentally-friendly hydrogenation catalyst.

Description: Poised to investigate the association of vanadium with physiological substrates in materials capable of exerting anticancer biological activity, pH-specific synthetic chemical reactivity between vanadium and triethyl ammonium acetate/trigonelline in aqueous and mixed organic-aqueous media led to the isolation of three new binary composite materials, namely K 2 [(MeN(+)C 5 H 4 COOH) 2 ][V 10 O 28 H 2 ] · 2H 2 O ( 1 ), [(H 2 N(+)Me 2 ) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 ( 2 ), and [(Me 3 N(+)CH 2 COOH) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 · 2H 2 O ( 3 ). 1–3 were characterized by elemental analysis, FT-IR and UV/Vis spectroscopy, Cyclic voltammetry, TGA-DTG, and X-ray crystallography. In all three compounds, the [V 10 O 28 H 2 ] 4– core unit is a common cluster assembly, with the vanadium in the +5 oxidation state. The counteracting cationic assembly in each composite material originates in the betaine starting reagent or the solvent out of which the materials crystallized. Biological activity studies of 1 and 3 in vitro in MCF-7 breast epithelial and A549 lung adenocarcinoma cell cultures show that both materials inhibit the viability of both cell lines in a dose-dependent fashion, in juxtaposition to the behavior of the betaine components present in these materials. Collectively, the herein studies a) reveal the uniquely defined synthetic methodologies and physicochemical properties of the variably assembled [V 10 O 28 H 2 ] 4– core units crystallized into the composite binary polyoxovanadate-betaine lattice structures, b) unravel the distinct cytotoxicity profile of the composite materials toward MCF-7 and A549 cells, and c) attest to their future potential as metallodrugs of pharmacological significance in anticancer activity.

Description: The crystal structures of the alkali aluminium thiohypodiphosphates M I AlP 2 S 6 (M I = Li, Na) are reported. NaAlP 2 S 6 crystallizes in the orthorhombic space group Fdd 2 (no. 43) with a = 8.0400(2), b = 10.9452(2), c = 20.8801(4) Å, and V = 1837.44(7) Å 3 ( Z = 8). It is isostructural with AgAlP 2 S 6 , which is consistent with the similar ionic radii of Na and Ag. In contrast, LiAlP 2 S 6 crystallizes in a different structure type which has not been observed in the large number of thiohypodiphosphates reported so far. It crystallizes in the monoclinic space group C 2/ c (no. 15) with a = 6.783(3), b = 10.365(4), c = 11.776(4) Å, β = 94.399(5)°, and V = 825.46(5) Å 3 ( Z = 4).

Description: We present the synthesis of 7-(diphenylphosphine)-indole 1 ( HPinol ) as a novel mono- and bidentate P - and N, P -ligand and its coordination chemical behaviour towards the d 6 - and d 8 -transition metals rhodium(III), palladium(II) and rhenium(I). The reaction of 1 with [Cp*RhCl 2 ] 2 in a 1:2 molar ratio leads to the formation of the P -coordinated complex [RhCl 2 ( P –( HPinol ))] ( 2 ). In the presence of the weak base NEt 3 , HCl elimination occurs by forming the neutral amido-phosphine chelated complex [RhCl( N, P –( Pinol ))] ( 3 ). The same P - and N, P -coordination is observed for palladium(II), where two ligands 1 coordinate to the metal centre forming the neutral complexes [PdCl 2 ( P – HPinol ) 2 ] ( 4 ) and [Pd( N, P – Pinol ) 2 ] ( 5 ). The reaction of Re(CO) 5 Br in the presence of NEt 3 and PPh 3 delivers the amido-phosphine complex [Re(CO) 3 PPh 3 ( N, P – Pinol )] ( 6 ). All products were characterised by multinuclear NMR spectroscopy, MS and IR spectra as well as elemental analysis. Furthermore, crystal structures of ligand 1 and all complexes 2–6 are presented.

Description: In the course of investigations relating to magnesia oxysulfate cement the basic magnesium salt hydrate 3Mg(OH) 2 · MgSO 4 · 8H 2 O (3–1–8 phase) was found as a metastable phase in the system Mg(OH) 2 -MgSO 4 -H 2 O at room temperature (the 5–1–2 phase is the stable phase) and was characterized by thermal analysis, Raman spectroscopy, and X-ray powder diffraction. The complex crystal structure of the 3–1–8 phase was determined from high resolution laboratory X-ray powder diffraction data [space group C 2/ c , Z = 4, a = 7.8956(1) Å, b = 9.8302(2) Å, c = 20.1769(2) Å, β = 96.2147(16)°, and V = 1556.84(4) Å 3 ]. In the crystal structure of the 3–1–8 phase, parallel double chains of edge-linked distorted Mg(OH 2 ) 2 (OH) 4 octahedra run along [–110] and [110] direction forming a pattern of crossed rods. Isolated SO 4 tetrahedra and interstitial water molecules separate the stacks of parallel double chains.

Description: The cover picture shows the synthesis and the molecular structure of a zwitterionic [4.3.0]-bicyclic aluminum-phosphorus compound with annulated C 3 P 2 and Al 2 C 2 PH heterocycles and a 3c-2e Al–H–Al bond. Treatment of the dialkynylphosphine Mes–P(–C=C–CMe 3 ) 2 ( 1 ) with diethylaluminum hydride ( 2 ) in an equimolar ratio afforded a mixture of compounds, in which a [3.2.0]-bicyclic compound 3 with annulated fourmembered AlC 2 P and five-membered P 2 C 3 heterocycles could be identified by NMR spectroscopy. Excess of the hydride 2 yielded small quantities of the zwitterionic [4.3.0]-bicyclic compound 4 , which formally resulted from the unique insertion of a diethylaluminum hydride molecule into the Al–C(vinyl) bond of the strained fourmembered heterocycle of 3 . A six-membered ring is formed which contains an Al–H–Al 3c-2e bond. More details can be found in the Article by Werner Uhl et al. on page 1181 ff.

Description: Using the bis(pyrazolyl)pyridinylmethane ligand α,α,α-bis(1-pyrazolyl)(2-pyridinyl)toluene {(ph)C(pz) 2 (py)} for bioinorganic inspired coordination chemistry studies, we synthesised and structurally characterised three monofacial complexes [{(ph)C(pz) 2 (py)}CoCl 2 ] ( C1 ), [{(ph)C(pz) 2 (py)}CuCl 2 ] ( C2 ), [{(ph)C(pz) 2 (py)}ZnCl 2 ] ( C3 ) and the binuclear halogenido-bridged complexes [{(ph)C(pz) 2 (py)} 2 (μ-Cl) 2 Fe 2 Cl 2 ] ( C4 ) and [{(ph)C(pz) 2 (py)} 2 (μ-Br) 2 Cu 2 Br 2 ] ( C5 ). In four of these complexes, severe disorders between pyrazolyl and pyridinyl donor groups are observed such that bis(pyrazolyl) and (pyrazolyl)(pyridinyl) coordination modes are concomitantly found. The donor competition is dissected by DFT calculation of the energy differences between the two coordination modes and NBO analysis of the donor situation. The pyrazolyl units provide with more donor strength although pyridine is considerably more basic.

Description: Metal ions poisoning can result from environmental factors, intentional action, or disruption of homeostasis. Although the origin of toxicity may be different, the treatment is similar. Chelation therapy aims to remove the excess of metal ions from tissues to stop further damage of cells. For almost every metal ion, molecules that are able to bind it and remove from the human body are known. Over the years some new chelating agents were discovered and introduced into clinical treatment. In this paper we have focused on typical chelators for metal ions, both essential and toxic for humans. The treatment of poisoning caused by essential metal ions is hard due to the risk of removing them from the biologically relevant molecules (e.g. enzymes). Acute metal ions poisoning is rather rare, so the development of chelators for such cases are historical, but prolonged toxicity of, especially, essential metal ions is extensively studied.

Description: The reactions of [Os(NO)Cl 5 ] 2– with glycine (GlyH), picolinic acid (PicoH), L -proline ( L -ProH) and D -proline ( D -ProH) afforded four novel complexes of the general formula [Os(NO)Cl 3 (AA)] – , where AA = Gly, Pico, L -Pro and D -Pro, respectively. X-ray diffraction studies have revealed that in all cases the same isomer type from three theoretically possible, has been isolated, namely mer (Cl), trans (NO, O)-[Os(NO)Cl 3 (AA)] – . Spectroscopic and electrochemical properties, behavior in aqueous solution and antiproliferative activity in three human cancer cell lines are also reported.

Description: The electron distributions in position and in momentum space of the hcp metals magnesium and zinc are investigated experimentally and compared to results of quantum-chemical calculations. Furthermore, a survey is given on recent analyses of the bonding properties of zinc and cadmium, using the method of increments. The experimental deformation densities were obtained by refining multipole models to X-ray diffraction data sets measured at 100 K with either Mo- K α (Mg) or Ag- K α (Zn) radiation. The final R F values (Valray/Jana2006) are 0.0028/0.0034 (Mg) and 0.0068/0.0068 (Zn). The differences to deformation densities obtained from periodic density functional calculations are discussed. The effect of dynamical electron correlation on the electron density was analyzed, using cluster models. Compton profiles were measured with 88.67 keV synchrotron radiation at beamline ID15B at the ESRF in Grenoble. Varied orientations of the samples allowed for probing the projected momentum distribution along the [100], [423] and [001] directions. Fourier transforms of the computed reciprocal form factor B ( r ) resulted in the corresponding theoretical Compton profiles. It is suggested that the anomalous hcp structure of zinc is favored by a kinetic balancing of the valence electrons, i.e. correlation mediated 4 s -3 d interactions.

Description: . This Research Report provides an overview on synthesis, structure, and reactivity of the recently discovered carboranylamidinate ligands. Carboranylamidinate anions of the type [( o -C 2 B 10 H 10 C(NHR)(=N R )] – ( R = i Pr, cyclohexyl) are readily accessible via addition of o -lithiocarborane to N , N ′-carbodiimides R –N=C=N– R . They combine the highly versatile characteristics of both amidinates and carboranes in one unique ligand system. Unlike simple amidinate anions, the carboranylamidinates coordinate to metal ions not as typical N , N ′-chelating ligands but adopt an unexpected κ 2 C, N -bonding mode. The free imine functionality in carboranylamidinates can be further deprotonated. The resulting dianions were demonstrated to be excellent starting materials for novel boron-rich heterocycles incorporating e.g. Si, Sn, P, or transition metals such as Ti, Zr, Rh, and Ir. Further modification of the carboranylamidinate cage structure includes the introduction of additional functional groups like –SH or –SeH as well as the selective removal of a boron atom with formation of novel nido -type dicarbollylamidinate ligands. An initial study already showed that transition metal carboranylamidinates are potentially useful as polymerization catalysts.

Description: KSbWO 6 was prepared by sol-gel method. N-doped KSbWO 6 (KSbWO 6– x N x ) was obtained by heating KSbWO 6 and urea at 400 °C. Both the compounds are characterized by powder X-ray diffraction (XRD), TEM, SEM-EDS, X-ray photo electronic spectroscopy (XPS), and UV/Vis diffuse reflectance spectroscopy (UV-DRS). A shift in the peak positions of powder XRD and XPS spectra was observed. The band gap energy ( E g ) of KSbWO 6 and N-doped KSbWO 6 was obtained from their diffused reflectance spectra. E g was reduced from 3.17 eV to 2.56 eV upon nitrogen doping in KSbWO 6 . The reduction of the E g is attributed to the lifting of valence band of N-doped KSbWO 6 , due to the mixing of O 2p states with N 2p states. The photocatalytic activity of both the samples was studied by degradation of methylene blue (MB). The nitrogen doped KSbWO 6 shows higher photocatalytic activity compared to that of KSbWO 6 .

Description: The chemistry of cytotoxic platinum(II) complexes is more or less restricted to ligand exchange reactions, derivatization of coordinated ligands is cumbersome, and subsequent purification in many cases impossible. Consequently, kinetically more inert platinum(IV) complexes found their way into the development of novel, promising anticancer drugs. Research has focused more and more during the last years on the use of platinum(IV) complexes featuring one or two axial succinato ligands in which one carboxylic acid moiety is available for further derivatization. In order to gain a deeper insight into the mechanism of action, isotopically labeled platinum(IV) complexes with axial (1,4– 13 C 2 )succinato ligands were synthesized and fully characterized by multinuclear ( 1 H, 13 C, 15 N, and 195 Pt) 1D- and 2D-NMR spectroscopy. Especially of note in this context is a long range 1 H, 13 C shift correlation signal detected between the equatorial ammine protons and the axially coordinated carboxylato moiety. Furthermore, their behavior in extracts of SW480 cancer cells was investigated. Preliminary results demonstrate that cisplatin analogs are reduced significantly faster in comparison to carboplatin analogs.

Description: The Cu II solution chemistry of synthetic derivatives of naturally occurring pseudo-octapeptides (patellamides and ascidiacyclamide) is described. The complex stabilities [mono- and dicopper(II) complexes] of five different ligands were determined by isothermal microcalorimetry (ITC), and square wave voltammetry (SQW) was used to elucidate the electrochemical properties. In agreement with published spectroscopic data, there is cooperative binding of two Cu II ions and the overall stabilities are, in agreement with known stabilities of the natural ligands and expectations based on the donor sets (two N-based heterocycles and one amide per Cu II ), only moderate ( K ≤ 10 6 ). There is a slight dependence of the stabilities on the ligand structure (configuration of the side chains), and that derived from the natural products forms the most stable complexes. Due to the complex equilibria in solution and the instability of the reduced forms, voltammetry shows complex equilibria, which preclude the full assignment of all processes. The positive reduction potentials are in agreement with relatively low complex stabilities. These observations complete earlier studies, concentrating on spectroscopy and structural aspects, and are also discussed in relation to the possible biological function of the cyclic peptides, i.e. metal ion transport, oxygen activation, carboanhydrase, and phosphatase activities.

Description: Setting out from protected L -cysteine a 2,5-diketopiperazine V can be synthesized, the reduction of which with NaBH 4 /TiCl 4 leads to (6 R ,8 aR )-7-methyl-6-(sulfanylmethyl)-thiazolidine [3,4- a ] piperazine, L 1 H as well as N , N ′-dimethyl-(2 R ,5 R )-bis(sulfanylmethyl) piperazine, L 2 H 2 , which were separated and characterized. L 2 H 2 can be obtained selectively, if V is reduced by NaBH 4 /TiCl 4 in the presence of DIEA · HCl, and it represents a precursor for a novel, chiral ligand, as after deprotonation it provides two thiolato and two amino donor functions for the coordination of a metal atom. Deprotonation of L 1 H and L 2 H 2 with NaOMe followed by treatment with NiBr 2 (dme) led to the isolation of the dimeric complexes [L 1 NiBr] 2 ( 1 ) and [L 2 Ni] 2 ( 2 ), respectively. Both were fully characterized, and cyclic voltammetry indicated the possibility of Ni II → Ni III oxidations for complex 2 . 2 can be regarded as a structural model for the A clusters of the acetyl coenzyme A synthase.

Description: A new chiral racemic ligand ( o -carboranyl)bis(2-hydroxymethyl)pyridine oCB(hmpH) 2 , that is composed of a central o -carborane unit where two arms radiate out of the cluster carbons each one containing a 2-pyridylmethylalcohol chelating arms, provides two potentially bidentate {NO} or one tetradentate {N 2 O 2 } binding pockets. An unprecedented octahedral Co II complex [CoCl 2 ( anti - oCB (hmpH) 2 ] was obtained under aerobic conditions and characterized by X-ray crystallography as well as IR and NMR spectroscopy. anti - oCB (hmpH) 2 acts as a tetradentate N 2 O 2 -ligand affording the complex as a racemic mixture of cis- α Δ-[CoCl 2 ( RR anti - oCB (hmpH) 2 )] and Λ-[CoCl 2 ( SS anti - oCB (hmpH) 2 )]. The new ligand oCB(hmpH) 2 appears to be suitable for producing a variety of new chiral-at-metal complexes.

Description: Abstract. The title compounds NH 4 [Cu(S 2 CNH 2 ) 2 ] · H 2 O (A) and CuS 2 CNH 2 (B) were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with copper sulfate in presence of excess cyanide as reductive. (A) crystallizes in the orthorhombic space group C 222 1 (No. 20) with a = 8.9518(6), b = 9.6414(6) and c = 10.6176(8) Å, Z = 4. (B) crystallizes in the orthorhombic space group P 2 1 2 1 2 1 (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = 9.4834(5) Å, Z = 4. In the crystal structure of (A) copper has a tetrahedral surrounding of four monodentate dithiocarbamate ligands. These structural units form 2D nets stacked along [001]. Staggered chains consisting of H 2 O and NH 4 + penetrate the crystal structure along [001] yielding additional coherence via hydrogen bonds. The crystal structure of (B) comprises a three-dimensional tetrahedral framework of CuS 4 units exclusively linked by vertices. The arrangement is reminiscent of a filled β -cristobalite structure with the dithiocarbamate ligands extending into the hollow spaces. Thermal decomposition precedes stepwise finally giving Cu 2 S in each case.

Description: A thorough study on the thermoelectric potential of the layered compound SnBi 2 Te 4 is presented. Phase range studies on SnBi 2 Te 4 , unit cell parameters by powder X-ray diffraction, and electronic structure calculations (both LDA and GGA functional) were performed. Physical property measurements regarding substitution of tin and bismuth with the triel ( Tr = Ga, In, Tl) elements are presented towards the improvement of thermoelectric properties, according to Tr x Sn 1– x Bi 2 Te 4 and Tr x SnBi 2– x Te 4 . The range of inclusion was generally over 0.01 ≤ x ≤ 0.15 to monitor compound changes as well as phase purity limits. Seebeck coefficient, S , electrical conductivity, σ , and thermal conductivity, κ , were measured, yielding the dimensionless Figure of merit, ZT , data over a temperature range between 300 K and 680 K. Results of partial replacements of tin and bismuth are compared and reported. ZT max values range from 0.10 to 0.34 depending on the dopant, achieved at temperatures from 355 K to 420 K.

Description: A new two-step procedure for the synthesis of MoS 2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS 2 +Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS 2 nanotubes (by using H 2 S gas in a reducing atmosphere at 820 °C). Unlike the case of WS 2 nanotubes, the synthesis of a pure phase of MoS 2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (〉800 °C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Description: The reaction of RuCl 2 (PPh 3 ) 3 with N -pyrazolylpropanamide ( N -ppa) displaces a single PPh 3 producing the six-coordinate complex RuCl 2 (PPh 3 ) 2 ( N -ppa) ( 1 ). A crystal structure determination of the dichloromethane solvate RuCl 2 (PPh 3 ) 2 ( N -ppa) · 2CH 2 Cl 2 ( 1·2CH 2 Cl 2 ) revealed that the geometry about the central Ru atom is distorted octahedral with the chloride ligands in trans -position and the N -ppa acting as N , O -chelating ligand. In the solid state, RuCl 2 (PPh 3 ) 2 ( N -ppa) molecules are dimerized via N–H ··· Cl hydrogen bonds. The dimers pack as chains in the c direction and form voids that are occupied by dichloromethane solvent molecules.

Description: Four complexes with supramolecular architectures, namely, MZCA · 3H 2 O ( 1 ), [Zn(H 2 O) 6 ] 2+ · [MZCA] 2 · [H 2 O] 6 ( 2 ), [Mn(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 3 ), and [Ni(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 4 ) [MZCA = 3-(carboxymethyl)-2, 7-dimethyl-3H-benzo[d]imidazole-5-carboxylic acid], were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complexes 1 and 2 display a remarkable 3D network with 1D hydrophilic channels. Complexes 3 and 4 are isostructural and exhibit a 3D structure encapsulating 1D 24-membered ring microporous channels. The UV/Vis and fluorescent spectra were measured to characterize complexes 1 – 4 . The thermal stability of complexes 2 – 4 were also examined.

Description: The transition metal dihydrogen hypodiphosphate hydrates K 2 [Co(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 1 ), K 2 [Ni(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 2 ), K 2 [Cu(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 3 ) and K 2 [Zn(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 4 ) were synthesized and characterized by single crystal structure determination. The compounds 1 – 4 crystallize isotypic in the monoclinic space group C 2/ m (no. 12) with two formula units in the unit cell. The crystal structure is built up by [H 2 P 2 O 6 ] 2– units in an eclipsed conformation, by the corresponding transition metal, potassium cations, and water molecules. The eclipsed conformation of the [H 2 P 2 O 6 ] 2– has not been previously observed in none of known hypodiphosphates(IV) analyzed via X-ray diffraction. However, its proposed based on spectroscopic methods. FT-IR/FIR and FT-Raman spectra of the crystalline salts were recorded and the thermal behavior of the compounds was investigated.

Description: Two coordination polymers, [Co 2 (Hcpip) 2 (phth)] n · 3 n (H 2 O) ( 1 ) and [Mn 2 (Hcpip) 2 (phth)] n ( 2 ), {H 2 cpip = 2-(2-carboxyphenyl)imidazo[4,5-f](1,10)- phenanthroline, H 2 phth = phthalic acid}, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complex 1 is a 1D chain, in which the dinuclear [Co 2 (Hcpip) 2 ] 2+ units are linked through (phth) 2– anions. Complex 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (phth) 2– anions. The magnetic properties of 1 and 2 show that the weak ferromagnetic interactions occurred between Co II ions in 1 and a weak antiferromagnetic interactions exist between Mn II ions in 2 . These two complexes have good thermal stabilities.

Description: Three tungsten oxychloride clusters containing the nearly D 3 d symmetric [(W 6 O 6 i Cl 6 i )Cl 6 a ] n – ( n = 2, 3) core were prepared from the cluster acid (H 5 O 2 ) 2 [W 6 O 6 Cl 12 ] · 4H 2 O and structurally characterized by single-crystal X-ray diffraction. The copper compound [Cu(H 2 O) 4 ][W 6 O 6 Cl 12 ] · 12H 2 O releases water molecules to yield [Cu(H 2 O) 6 ][W 6 O 6 Cl 12 ]. Both compounds are represented as diamagnetic clusters, having 14 electrons in W–W bonding states. Magnetic measurements on the calcium compound [Ca(H 2 O) 7 ] 2 [W 6 O 6 Cl 12 ]Cl revealed a paramagnetic cluster having 15 valence electrons.

Description: Phase equilibrium in the Ca-Mn-Sb-O system was studied in air at the temperature range from 1160 to 1250 °C and a pseudo-quaternary phase diagram for the system CaO-MnO-Mn 2 O 3 -Sb 2 O 5 is presented. The following compounds were discovered: new antimonate Ca 7 Sb 2 O 12 with a perovskite-like structure, solid solutions Mn 2– x Ca x Sb 2 O 7 (0 ≤ x ≤ 1.6) with a 3 T -weberite structure, and Ca 2– x Mn x Sb 2 O 7 (0 ≤ x ≤ 0.23) with a 2 O -weberite structure, as well as solid solutions Ca 2 Mn 1+ x Sb 1– x O 6 with monoclinic (0 ≤ x ≤ 0.67) and orthorhombic (0.75 ≤ x ≤ 1) perovskite structures. The existence of a number of double and ternary oxides and solid solutions on the basis of Sb 5+ and Mn 2+ , Mn 3+ , Mn 4+ and with mixed manganese valence is confirmed.

Description: The reaction of LAlMe 2 ( 1 ) [L = HC(CMeNAr) 2 , Ar = 2,6- i Pr 2 C 6 H 3 ] with diphenylstannanediol resulted in the methylalumoxane compound L(Me)Al(μ-O)Al(Me)L ( 3 ). Compound (LAlO) 2 B(2, 6-OCH 3 C 6 H 4 )(μ-O) ( 4 ) containing the Al 2 BO 3 six-membered ring was accomplished by reacting the precursor LAlH 2 ( 2 ) with 2,6-dimethoxyphenylboronic acid. The two compounds were characterized by 1 H NMR spectroscopy, elemental analysis, and single-crystal X-ray structural analysis.

Description: A novel fairly stable N -trimethylsilylamino(dichloro)phosphine was prepared, in which the nitrogen atom bears a 9-borabicyclo[3.3.1]nonyl group. The gas phase structures of various amino- and silylaminophosphines including a phosphenium cation and an amino(imono)phosphine were optimized at the B3LYP/6-311+G(d, p) level of theory, and NMR parameters were calculated. Both magnitude and sign of the two-bond coupling constants 2 J ( 31 P, N, 13 C) and 2 J ( 31 P, N, 29 Si), known to be sensitive towards the respective conformation, are well reproduced by the calculations. This also holds for 1 J ( 31 P, 15 N), although calculated values 1 K ( 31 P, 15 N) (all 〈 0) are slightly more negative [ 1 J ( 31 P, 15 N) more positive] than experimental values.

Description: A new synthetic entry to iridium Keggin-type polyoxometalate complexes from [PW 11 O 39 ] 7– and K 3 [IrCl 6 ] under harsh conditions is reported. The complex [PW 11 O 39 IrCl] 5– ( 1 5– ) featuring an IrCl functionality was obtained in high yield and characterized by NMR spectroscopic and ESI-MS techniques. The presence of Li + (3–4 M) is essential for a quantitative yield of 1 5– . The reactivities of 1 5– and its rhodium analogue [PW 11 O 39 RhCl] 5– in ligand substitution at the noble metal site were studied. Thiocyanate coordination successfully yielded (Bu 4 N) 5 [PW 11 O 39 M (SCN)] [ M = Rh ( 2a ), Ir, ( 3a )]. In both cases, the SCN ligands are coordinated by sulfur atoms, according to 13 C NMR and IR spectroscopic data. Gas-phase fragmentation reactions of compounds 2a and 3a were also investigated by collision-induced dissociation (CID) experiments. Reaction of [PW 11 O 39 RhCl] 5– with NaN 3 resulted in Cl – to OH – replacement accompanied by the liberation of the RhCl fragment, whereas 1 5– proved unreactive with NaN 3 . Attempts to coordinate NO 2 – are adversely affected by competing noble metal excision with formation of free [PW 11 O 39 ] 7– .

Description: Four discrete metal-radical complexes, [Cu( p -MePh-COO) 2 (NITpPy) 2 ] ( 1 ), [Ni( m -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] · (CH 3 -OH) 2 ( 2 ), [Mn( p -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] ( 3 ), and [Mn( m -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] ( 4 ) [NITpPy = 2-(4-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide] were synthesized and characterized by elemental analyses, IR spectroscopy, PXRD, single-crystal X-ray diffraction, and magnetic susceptibility. For the four complexes, the crystal structural analyses indicate that the two radical ligands coordinated to the metal ions by the nitrogen atoms of the pyridine rings form three spin complexes, where toluates act as co-ligands. Weak antiferromagnetic interactions [ J Cu–Rad = –6.75 cm –1 ( 1 ), J Co–Rad = –4.15 cm –1 ( 2 ), J Mn–Rad = –0.22 cm –1 ( 3 ), and J Mn–Rad = –3.74 cm –1 ( 4 )] were observed, spin polarization mechanism and orbital symmetry are used to explain the magnetic coupling in these complexes.

Description: The new ternary compounds UP 2 S 6 , UP 2 S 7 , U(P 2 S 6 ) 2 , and U 3 (PS 4 ) 4 were prepared from uranium metal, phosphorus pentasulfide, and sulfur at 700 °C. The crystal structures were determined by single-crystal X-ray diffraction methods. UP 2 S 6 ( I ) crystallizes in the ZrP 2 S 6 structure type [tetragonal, P 4 2 / m , a = 6.8058(7) Å, c = 9.7597(14) Å, Z = 2], which consists of central uranium(IV) atoms coordinated by P 2 S 6 4– anions (staggered conformation). The anions are two-dimensional connectors for four uranium cations arranged in one plane. The structure of UP 2 S 7 ( II ) [orthorhombic, Fddd , a = 8.9966(15) Å, b = 15.2869(2) Å, c = 30.3195(5) Å, Z = 16] is closely related to the monoclinic ZrP 2 S 7 structure type. It consists of U 4+ cations linked by P 2 S 7 4– ligands, the resulting 3D network contains large pores (diameter approx. 3.5 × 16.7 Å). In the previously reported compound U(P 2 S 6 ) 2 ( III ) [ I 4 1 / a , a = 12.8776(9) Å, c = 9.8367(10) Å, Z = 2], the metal atoms are coordinated by four bidentate P 2 S 6 2– ligands. This arrangement can be considered as a pseudotetrahedral coordination of the uranium atoms by the linear ligands. Three of the resulting diamondoid frameworks are inseparably interwoven in order to optimize space filling. U 3 (PS 4 ) 4 ( IV ) [ I 4 1 / acd , a = 10.7440(9) Å, c = 19.0969(2) Å, Z = 2] crystallizes in a defect variant of the PrPS 4 structure type, with 50 % of the U2 sites statistically occupied with uranium atoms. The resulting stoichiometry is U 3 (PS 4 ) 4 with tetravalent uranium atoms. The structure of U 3 (PS 4 ) 4 consists of uranium atoms connected by PS 4 3– groups, each PS 4 group linking four central uranium atoms. Vibrational spectra, which were recorded for I – III , show good agreement between the obtained results and the expected values for the anionic units, while magnetic measurements confirm the presence of tetravalent uranium.

Description: 2-Pivaloylpterin, an acylated derivative of the biochemically relevant pterin [2-amino-4-oxo-(3 H )pteridine] heterocyclus, undergoes stepwise metallation by the 1, 1′-bis(diphenylphosphanyl)ferrocene-copper(I) cation, [(dppf)Cu] + . The final product obtained, [Cu 3 (dppf)(μ 2 -dppf)(PP)(PP-H + )] 2 (BF 4 ) 4 , could be structurally characterized to reveal coordinative saturation with binding of central Cu + ions to N 1 ,N 3 ,O 4 ,N 5 ,N 8 and pivaloyl-O donor atoms.

Description: Abstract . Two coordination polymers, namely, {[Cd(cdpc)(hmt)(H 2 O)] · H 2 O} n ( 1 ), and [Mn(Hcdpc) 2 (4, 4′-bpy)(H 2 O)] n ( 2 ), were constructed by synergistic assembly through the mixed-ligand synthetic strategy (H 2 cdpc = 1-carboxymethyl-3, 5-dimethyl-1H-pyrazole-4-carboxylic acid, hmt = hexamethylenetetramine, and 4, 4′-bpy = 4, 4′-dipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X-ray diffraction analysis reveals that complex 1 is a 2D 4-connected sql sheet, and complex 2 is an interesting 1D loop chain. The two complexes are further expanded to 3D supramolecular structure through non-covalent bonds. Besides, luminescent properties of two complexes in the solid state and magnetic property of 2 were also investigated.

Description: The chemical preparation, structure, luminescence, and electronic properties are given for a new potassium holmium cyclotetraphosphate KHoP 4 O 12 , a promising optics material for applications. Single-crystal X-ray diffraction analysis shows that the newly synthesized compound crystallizes in the monoclinic system with space group C 2/ c and Z = 4. [P 4 O 12 ] 4– anionic rings and HoO 8 polyhedra display a three-dimensional (3D) framework by corner-sharing. The ten-coordinated potassium atoms are located in the delimited tunnels. KHoP 4 O 12 exhibits the blue light emission under the excitation of 330 nm. To gain further insights into electronic properties of crystal KHoP 4 O 12 , theoretical calculation based on density functional theory (DFT) was performed using the total-energy code CASTEP with the LDA + U approach. The calculated bandgap with U = 3.0–3.5 eV is in good agreement with the experimental measurement.

Description: The facile synthesis, molecular structure, and reactivity of [Cu(C 7 H 7 NH 2 )Cl] 4 ( 1 ) towards dioxygen and derivatives is reported. The compound could easily be prepared in good yields by mixing CuCl and benzylamine under inert conditions in dichloromethane. Surprisingly this copper(I) compound, a copper(I) tetramer with Cu I ··· Cu I interactions of 2.89 Å, was formed instead of an expected cubane cluster. Oxidation reactions led to formation of μ-oxido-species as intermediates, however 1 did not show any catalytic activity in the activation of CH bonds. In contrast it turned out that 1 was quite stable towards oxidation. Analogous reactions with CuBr or CuI were different and neither cluster units or polynuclear copper(I) complexes were obtained.

Description: The effect of different factors, such as pH of the medium (1.5 〈 pH 〈 4.0; 1 × 10 –4 mol · L –1 〈 [SO 4 2– ] 〈 1 × 10 –1 mol · L –1 ), the concentration of extracting agent, temperature and the type of the solvent, on the extraction of vanadium(V) by trioctylamine was studied. It was shown that the extraction of vanadium(V) by trioctylamine at 25 ± 0.5 °C takes place in the pH range 2.0–3.5 and the extracting complex contains decavanadate anion H 2 V 10 O 28 4– and four molecules of the extracting agent. This allows the reaction of vanadium(V) extraction by trioctylamine to be described by the following equation: 2( R 3 NH) 2 SO 4 + H 2 V 10 O 28 4– ( R 3 NH) 4 H 2 V 10 O 28 + 2SO 4 . The effect of the length of the alkyl chain of alcohol (propyl, butyl, isododecyl alcohol) on the homogeneity of the system V V -TOA-toluene-alcohol was investigated. It was established that the solubility of the extracting complexes of vanadium(V) with trioctylamine can be increased by using isododecyl alcohol C 12 H 25 OH as a modifying agent. It was shown that under optimal conditions in the presence of isododecyl alcohol at temperatures above 25 °C in the pH interval 2.0–3.5 trioctylamine extracts vanadium(V) with a high distribution coefficient (lg D V V 〉 2).

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 tetraalkyldigallium(II) compound R 2 Ga–Ga R 2 ( 1 ) [ R = CH(SiMe 3 ) 2 ] reacted with amino and hydroxo functionalized carboxylic acids by retention of the Ga–Ga bond and release of CH 2 (SiMe 3 ) 2 . New heterocyclic or cage-like compounds were formed with three, two, or six Ga–Ga bonds in a single molecule. The latter dodecagallium compounds encapsulated THF or dioxane molecules in their molecular cavities (carcerands), the other compounds have up to six THF molecules coordinated by N–H ··· O hydrogen bonds.

Description: Reduction of chalcogen-rich Pb:Ch (1:2) phases in ethane-1,2-diamine ( en ) by elemental alkali metals results in the formation of solutions of [Pb 2 Ch 3 ] 2– of high purity and abundance. In contrast, application of the same reaction conditions to a binary Bi:Te (1:2) phase yields the mononuclear [BiTe 3 ] 3– anion. Instead of the expected [Tl 2 Te 3 ] 4– or [Tl 2 Te 2 ] 2– anions, analogous reactions with a Tl:Te (1:1) phase end up with a C–C-bond cleavage of the solvent en with formation of a salt of the telluridocyanate (N≡C–Te) – anion. Side reactions of en and elemental cesium are presented and metalate solutions are investigated with NMR spectroscopy.

Description: Seven lanthanide containing strand-like coordination polymers and dimeric complexes were obtained in a reversible reaction from 1, 3-thiazole (thz) and Ln Cl 3 ( Ln = La, Ce, Pr, Nd). The reactions do not require activation and render coordination polymers accessible at room temperature, already. The product constitutions depend on the lanthanide and the thiazole-to-halide ratio. For lanthanum and cerium formation of the coordination polymers 1 ∞ [ Ln Cl 3 (thz) 3 ] · thz as well as dimeric complexes [ Ln 2 Cl 6 (thz) 8 ] · 3thz were observed. For praseodymium and neodymium dimeric complexes were observed with and without non-coordinating thz. Upon heating, the compounds release thiazole under re-formation of Ln Cl 3 , the formation reaction thus being a thermally reversible reaction. Compounds and conversion processes were characterized by temperature dependent X-ray powder and single-crystal X-ray diffraction, in-situ temperature dependent gas phase IR spectroscopy, DTA/TG, and elemental analysis.

Description: The structural and vibrational data for the CF 3 XX CF 3 ( X = O, S, Se, Te) molecules were compared using DFT quantum chemistry calculations. The experimental vibrational frequencies and their assignments to the different normal modes of vibration could be confirmed. The data was also used to define a scaled quantum mechanics force field and sets of derived internal force constants for each molecule. A linear relationship between the experimental X – X bond lengths and the corresponding force constants was found. Additionally, some calculations for the mixed molecule CF 3 SOCF 3 were made.

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.