ALBERT

Description: Single crystals of Sr[B(C 6 H 5 O 7 ) 2 ](H 2 O) 4 · 3H 2 O, a new borate-citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C 6 H 5 O 7 ) 2 ](H 2 O) 4 · 3H 2 O was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P 2 1 / c , with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO 8 dodecahedra, BO 4 tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis.

Description: Two new polymeric iodoargentate hybrids induced by rare earth metal complexes and conjugated organic cations, {[Er(DMF) 8 ][Ag 6 I 9 ]} n ( 1 ) and [(MMP)(AgI 2 )] n ( 2 ) (MMP = 1-methyl-4-methylpyridinium) were obtained by the routine synthetic reaction and structurally determined. In compound 1 , a (Ag 6 I 9 ) n 3 n – chain is defined by edge-sharing Ag 6 I 12 units, and in 2 , the (Ag 2 I 4 ) n 2– chains are constructed by edge-sharing AgI 4 tetrahedra. C–H ··· I hydrogen bonds between cations and iodoargentate polyanions contribute to their structural extension from 1D to a 2D layer (for 1 ) and a 3D network (for 2 ). The UV/Vis spectra indicate that compared with 2 , compound 1 exhibits a narrower adsorption scope with an onset at about 360 nm, and it has a much wider bandgap of about 3.50 eV.

Description: The synthesis of two new diphosphonic acid ligands, [ethane-1, 2-diylbis(azanediyl)]bis[(4-chlorophenyl)methylene]diphosphonic acid (L 1 P), [ethane-1, 2-diylbis(azanediyl)]bis[(4-bromophenyl)methylene]diphosphonic acid (L 2 P), and their corresponding copper complexes, Cu 2 (L 1 P) 2 ( 1 ) and Cu 2 (L 2 P) 2 ( 2 ) are described herein. Complex 2 was structurally characterized with X-ray single crystal diffraction. The structure of 2 consists of five-coordinate copper(II) ions with a distorted square pyramidal arrangement doubly bridged by OPO from phosphonate groups. The Cu–Cu distance is 4.7810(2) Å. The crystal packing is determined by interdinuclear hydrogen bonds, which lead to one-dimensional chains. The results of thermogravimetric investigations (TG-DTA), UV/Vis diffuse reflectance, infrared and ( 1 H and 13 C) NMR spectroscopy, as well as elemental analyses of compounds 1 and 2 are also presented.

Description: A series of [Mn 6 O 2 ( R 1 OH) 4 (sao) 6 ( R 2 COO) 2 ] complexes with terminal functional groups ( 1 : R 1 = CH 3 , R 2 = HO-C 6 H 4 , 2 : R 1 = C 2 H 5 , R 2 = H 2 N-C 6 H 4 , 3 : R 1 = CH 3 , R 2 = Cl-C 6 H 4 , 4 : R 1 = CH 3 , R 2 = CH 3 S-C 6 H 4 , 5 : R 1 = CH 3 , R 2 = I-C 6 H 4 , 6 : R 1 = CH 3 , R 2 = pymSCH 2 , 7 : R 1 = CH 3 , R 2 = ortho -pyr-SCH 3 , 8 : R 1 = C 2 H 5 , R 2 = (CH 3 ) 3 OOCNHCH 2 C 6 H 4 ; sao = doubly deprotonated salicylaldoxime ligand, pym = pyrimidyl, pyr = pyridyl) have been obtained in a reaction of a ligand R 2 C 6 H 4 COOH, salicylaldoxime, manganese(II) perchlorate and [NEt 4 ](OH) in methanol or a 1:1 mixture of ethanol and dichloromethane. In this report, structural aspects as well as preliminary studies of magnetic and thermal properties are presented. Compounds 1 , 3 , 6 , 8 exhibit an antiferromagnetic coupling of the Mn 2+ ions, whereas 4 and 7 show ferromagnetic interactions. The title compounds may act as starting materials for further derivatization addressing the functional groups.

Description: The reaction of (NH 4 ) 2 PbCl 6 and fuming sulfuric acid (65 % SO 3 ) in a sealed glass tube at 250 °C led to colorless single crystals of Pb[S 3 O 10 ] (orthorhombic, Pbcn , Z = 4, a = 10.9908(4), b = 8.5549(3), c = 8.0130(3) Å, V = 753.42(5) Å 3 ). The compound shows a three-dimensional linkage of the tenfold oxygen coordinated Pb 2+ ions and exhibits the unusual trisulfate anion, [S 3 O 10 ] 2– , that consists of three vertex connected [SO 4 ] tetrahedra. The distances S–O within the S–O–S bridges of the anion are remarkable asymmetric with distances of 155 and 169 pm, respectively. This structural feature is well reproduced by calculations on a PBE0/cc-pVTZ and a MP2/cc-pVTZ level of theory. Similar calculations allow also for an inspection of the yet unknown corresponding acid, H 2 S 3 O 10 . Also for this acid non-symmetric S–O–S bridges are predicted. The thermal behavior of Pb[S 3 O 10 ] is characterized by the loss of two equivalents of SO 3 at low temperature and the decomposition of intermediate Pb[SO 4 ] at higher temperature.

Description: The title ligand, [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazene, H L ( 1 ), was prepared. In a reaction with Hg(NO 3 ) 2 it forms the complex [Hg(C 26 H 22 Cl 2 N 6 O 2 )], [Hg L 2 ] ( 2 ). Both compounds were characterized by means of X-ray crystallography, CHN analysis, FT-IR, 1 H NMR, and 13 C NMR spectroscopy. In the structure of compound 1 , two independent fragments are present in the unit cell. They exhibit trans arrangement about the –N=N– double bond. The dihedral angles between two benzene rings in both fragments are 4.36 and 18.79 Å, respectively. Non-classic C–H ··· N hydrogen bonding and C–H ··· π interactions form a layer structure along the crystallographic ab plane [110]. In compound 2 , the Hg II atom is hexacoordinated by two tridentate [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazenide ligands through a N 2 O 2 set. In addition, in the structure of 2 , monomeric complexes are connected to each other by C–H ··· π stacking interactions, resulting in a 2D architecture. These C–H ··· π edge-to-face interactions are present with H ··· π distances of 3.156 and 3.027 Å. The results of studies of the stoichiometry and formation of complex 2 in methanol solution were found to support its solid state stoichiometry.

Description: The antimony aminoalkoxide and aminothiolates Sb( E CH 2 CH 2 NMe 2 ) 3 [ E = O ( 1 ), S ( 2 )] were synthesized and their ability to form adducts with other metal moieties investigated. Compound 1 forms 1:1 adducts with NiI 2 ( 3 ) and M (acac) 2 [ M = Cd ( 4 ), Ni ( 5 )], while 2 undergoes ligand exchange with AlMe 3 to afford Me 2 AlSCH 2 CH 2 NMe 2 ( 6 ). The structures of 2 – 4 and 6 were determined. Compound 2 incorporates three S, N -chelating ligands though the interaction with nitrogen is weaker than in analogous alkoxide complexes. Product 3 reveals one iodine has migrated from nickel to antimony, and all three alkoxide ligands bridge the two metals through μ 2 -O atoms. In contrast, in 4 , only one alkoxide links the antimony and cadmium. Compound 6 adopts the same structure, a chelating S , N ligand generating a tetrahedral center at aluminum, as known t Bu 2 AlSCH 2 CH 2 N R 2 species ( R = Me, Et).

Description: Reaction of 2, 4, 6-tri- tert -butylphenol ( 1 ) with di- n -butylmagnesium in the molar ratio 1:1 allows the synthesis of {( n Bu)Mg( μ -O R ) 2 Mg( n Bu)} ( 2 ) ( R = 2, 4, 6- t Bu 3 C 6 H 2 ), which reacts with excess 1 to give the homoleptic alcoholate complex {( R O)Mg(μ-O R ) 2 Mg(O R )} ( 3 ) ( R = 2, 4, 6- t Bu 3 C 6 H 2 ). The structures of 2 and 3 were determined by X-ray crystallography.

Description: Three pyrotechnic compositions based on ytterbium /polytetrafluoroethylene/Viton ® ( YTV ) 77/18/5, 82/13/5 and 87/8/5 wt.-% were compared to a baseline magnesium /polytetrafluoroethylene/Viton® ( MTV ) 60/35/5 wt.-% composition. YTV though energetically inferior to MTV both gravimetrically and volumetrically exhibit a radiance L λ (W · sr –1 · cm –2 ) superior to MTV in the important beta-band ( λ = 3.5–4.6 μm). This is assumed to be due to the selective emissivity of Yb 2 O 3 which is formed in the afterburning zone of YTV. The emissivity of Yb 2 O 3 is 7–10 times higher than that of MgO in the same spectral range. Due to the high density of ytterbium and the formulations based thereon YTV are promising candidates for autophagous nose cones for kinematic blackbody flares.

Description: Na 2 SO 4 BF 3 , synthesized in a closed vessel from BF 3 and Na 2 SO 4 at 603 K, crystallizes in the triclinic space group P ( a = 6.6033(2), b = 6.6328(2), c = 6.6349 (1) Å, α = 84.542(2), β = 84.458(1) and γ = 65.762(1)°). The novel fluorooxo anion [SO 4 BF 3 ] 2– displays a structure similar to the disulfate anion S 2 O 7 2– . Heating the title compound in the absence of BF 3 in the gas phase leads to decomposition even at 553 K, which is below the temperature of synthesis under BF 3 pressure.

Description: Non-cyclic and cyclic silyl-substituted 1, 2-dicarba- closo -dodecaborane(12) derivatives were prepared mainly by salt elimination methods. Several known and new compounds were structurally characterized by X-ray analysis in the solid state and by mulinuclear magnetic resonance ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR) in solution. This includes the 1, 2-bis(trimethylsilyl) and 1, 2-bis(chlorodimethylsilyl) derivatives as examples for non-cyclic compounds and a series of 1, 1, 3, 3-tetramethyl-4, 5-[1, 2-dicarba- closo -dodecaborano(12)]-1, 3-disila-2-element-cyclopentanes (element = S, Se, Te). Numerous spin-spin coupling constants were determined together with their signs. Molecular gas phase geometries for most compounds studied were optimized by calculations [B3Lyp/6-311+G(d, p)], and NMR parameters were calculated at the same level of theory. The conversion of silyl-substituted ortho -carboranes into their respective 7, 8-dicarba- nido -undecaborate(1-) derivatives was explored successfully for several examples.

Description: Clara Immerwahr was a talented chemist born at the end of the 19th century. In 1900, she received the first doctorate in chemistry awarded to a woman candidate at Breslau University, Germany. She married Nobel Laureate Fritz Haber and vehemently opposed his well-known work on chemical warfare during WWI. Popular works, including theater and documentary film, dramatize her dilemma in a way that can catalyze meaningful discussion in college-level chemistry courses on scientists' ethical and civic responsibilities. This paper surveys her life, accomplishments in chemistry, and her legacy.

Description: During attempts to synthesize lanthanoid(III) fluoride oxoselenates(IV) with the simple composition M F[SeO 3 ], not only Pr 3 F[SeO 3 ] 4 , but also Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 appeared as pale green crystalline by-products in the case of praseodymium. Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 crystallizes triclinically in space group P (no. 2) with a = 701.14(5), b = 982.68(7), c = 1286.79(9) pm, α = 70.552(3), β = 76.904(3), γ = 69.417(3)° and Z = 2. The five crystallographically different Pr 3+ cations on the general positions 2 i show coordination numbers of eight and nine. [(Pr1)O 8 ] 13– and [(Pr2)O 8 ] 13– polyhedra are connected to {[(Pr1, 2) 2 O 12 ] 18– } chains along the [100] direction. [(Pr3)O 7 F] 12– , [(Pr4)O 8 F] 14– and [(Pr4)O 8 F] 14– polyhedra generate [F(Pr3, 4, 5) 3 O 19 ] 30– units about their central F – anion in triangular Pr 3+ coordination. These units form {[F(Pr3, 4, 5) 3 O 16 ] 24– } strands, again running parallel to [100]. Their alternating connection with the {[(Pr1, 2) 2 O 12 ] 18– } chains results in {[Pr 5 O 20 F] 26– } sheets parallel to the (001) plane. Like in the already known related compound Er 3 F[SiO 4 ][SeO 3 ] 2 , a three-dimensional network {[Pr 5 O 17 F] 20– } is achieved without the contribution of both the tetravalent silicon and selenium components. However, two Si 4+ and three Se 4+ cations forming tetrahedral [SiO 4 ] 4– and ψ 1 -tetrahedral [SeO 3 ] 2– units with all O 2– anions guarantee the charge balance. The formation of Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 was observed when praseodymium sesquioxide (Pr 2 O 3 : in-situ produced from Pr and Pr 6 O 11 in a molar ratio of 3 / 11 : 4 / 11 ),praseodymium trifluoride (PrF 3 ) and selenium dioxide (SeO 2 ) in 1:1:3 molar ratios were reacted with CsBr as fluxing agent for five days at 750 °C in evacuated fused silica (SiO 2 ) ampoules.

Description: The cover picture shows the structure of the uranium thiophosphate CsLiU(PS 4 ) 2 , which has been synthesized by reacting uranium metal, Cs 2 S, Li 2 S, S and P 2 S 5 at 700�C. The crystal structure was determined by single crystal X-ray diffraction. CsLiU(PS 4 ) 2 crystallizes in the rhombohedral space group R c (a = 15.2797(7) Å; c = 28.778(2) Å, V = 5818.7(5) Å 3 , Z = 18). The structure of contains a unique three-dimensional U(PS 4 ) 2 2– framework with large tunnels having an approximate diameter of 6.6 Å running parallel to the crystallographic c axis. The tunnels are filled with Cs + cations. The smaller Li + cations are located at tetrahedral sites at the periphery of the channels. In the structure of CsLiU(PS 4 ) 2 the uranium atoms are coordinated by thiophosphate groups in a pseudotetrahedral fashion, and the PS 4 groups act as linear connectors. Topologically, CsLiU(PS 4 ) 2 may be regarded a chalcogenide analogue of silicate frameworks, with the uranium atoms and PS 4 groups replacing silicon and oxygen atoms. More details are discussed in the article by Wolfgang Tremel et al. on pp. 405ff.

Description: Alanes of the formula H x Al X 3– x ( x = 0, 1, 2, 3; X = Cl, Br, I) and the mixed halogen species HAlClBr were synthesized as N -methyl-piperidin (nmp) adducts H x AlX 3– x · z nmp ( z = 1, 2) and HAlClBr · 2nmp by different routes. The crystal and molecular structures of (H 3 Al · nmp) 2 , H 2 AlBr · 2nmp, H 2 AlI · 2nmp, the isotypic and isomorphous HAlBr 2 · 2nmp, HAlI 2 · 2nmp, as well as ACl 3 · nmp, ABr 3 · nmp, AI 3 · nmp, and HAlClBr · 2nmp are described. The aluminum atoms in these molecular structures either form a pentagonal bipyramid as coordination sphere with the amine bases in apical positions or are in the center of a distorted tetrahedron (AlCl 3 · nmp, ABr 3 · nmp, AI 3 · nmp). In the nmp adduct of alane, a central Al 2 H 2 ring is formed by dimerisation of AlH 3 , each aluminum atom displaying a further nmp ligand together with two terminal hydrogen atoms. The influence of the halogen atoms on the hydrogen bonds in the iso-structural compounds were studied by IR spectroscopy, showing in both series H 2 Al X · 2nmp and HAl X 2 · 2nmp ( X = Cl, Br, I) a dependence of ν(Al–H) on the substitution pattern: 1770.2–1775.2–(not measured) cm –1 (H 2 Al X ) and 1785.0–1788.0–1791.0 cm –1 (HAl X 2 ). The δ values of the 27 Al-NMR spectra in solution show dependences on the halide numbers bonded to aluminum and display a regular growth with heavier element in the H 2 Al X · 2nmp series δ ( 27 Al): 121.2 (Cl), 126.0 (Br), 131.5 (I)], whereas they have an unsteady evolution in the HAl X 2 · 2nmp series [δ ( 27 Al): 118.0 (Cl), 122.0 (Br), 108.0 (I)] and the Al X 3 · nmp series [δ ( 27 Al): 102.1 (Cl), 104.8 (Br), 61.9 (I)].

Description: A new synthesis route to Li 2 NiF 4 based on a fluorolytic process using Ni(acac) 2 or Ni(OAc) 2 · 4H 2 O as precursor is presented. Variation of the synthesis conditions allows crystallite size control of the obtained powders. 6 Li and 7 Li MAS NMR experiments were carried out to study local environments of the lithium ions. Several attempts were made to synthesize Li 2 CoF 4 , which are, unfortunately, hitherto not successful. Nevertheless, our studies clearly reveal that solid solutions Li 2 NiF 4 –Li 2 CoF 4 are stable up to ca. 30 % cobalt. High-temperature X-ray diffraction measurements also show no evidence for the existence of pure Li 2 CoF 4 . These findings are supported by quantum chemical calculations.

Description: The cover picture shows the binary chalcogenidotetrelate building blocks [TE 4 ] 4– and [(RT) 4 E 6 ] that were used to generate the rich variety of compounds depicted around them. In their perspective article Dehnen et al. describe a stepwise coordination chemistry approach, allowing the sequential formation of multinary chalcogenidometallates and intricate organofunctionalized clusters, starting from these simple precursors The article outlines structure types, factors influencing the formation of specific structures and the properties of the resulting materials, and can be found on pages 2425 ff.

Description: New gold(III) carboxylate complexes [(L)Au( R CO 2 ) 2 ]BF 4 ( R = CH 3 , CMe 3 , CF 3 ) with N, N-chelating ligands L (L = phenanthroline, 2, 2′-bipyridine), were obtained by the treatment of corresponding chloride complexes [(L)AuCl 2 ]BF 4 with silver(I) carboxylates. The structure of [(bipy)Au(CF 3 CO 2 ) 2 ]BF 4 complex was determined by X-ray diffraction analysis. When five-coordinate gold(III) complexes [(L)AuCl 3 ] (L = 2, 9-dimethyl-1, 10-phenanthroline, 2, 2′-biquinoline) were used as starting materials the same reaction led to unstable products, which could not to be isolated and characterized. The reactivity of chloride complexes towards different carboxylates as well as properties of resulting carboxylate compounds depends on the nature of substitute R in carboxylate groups as it was predicted by us earlier using quantum-chemical calculations. In order to explain a difference in behaviors of four- and five-coordinate gold(III) complexes infrared and far-infrared spectra of chlorides and carboxylates were studied.

Description: Two Cu II complexes of tridentate Schiff base ligands, [Cu(L 1 )(CH 3 OH) 2 ]NO 3 · CH 3 OH ( 1 ) and [Cu 2 (L 2 ) 2 (CH 3 OH) 2 ](NO 3 ) 2 ( 2 ), were prepared and characterized by elemental analyses and spectroscopic methods [H 2 L 1 = ( E )- N -(4-hydroxy benzoic acid (2-hydroxy-3-methoxybenzylidene)benzohydrazide, and H 2 L 2 = ( E )- N -4-hydroxy benzoic acid (5-bromo-2-hydroxybenzylidene)benzohydrazide]. The crystal structures of 1 and 2 were established by X-ray crystallography. The complex cation in 1 is based on a square pyramid with the uninegative Schiff base coordinating in a tridentate mode via O, N, O′-donor atoms with the remaining sites being occupied by two methanol oxygen atoms with one of these in the axial position. By contrast, the Schiff base coordinates in a tridentate ligand fashion in dinuclear compound 2 as the phenoxide oxygen atom bridges two central copper atoms. The NO 4 coordination donor set is completed by a methanol oxygen atom, which occupies an axial position in the distorted square pyramidal arrangement. Complexes 1 and 2 are very active catalysts in clean epoxidation reactions using aqueous hydrogen peroxide and acetonitrile. The effects of reaction parameters such as solvent and oxidant in the epoxidation of cis -cyclooctene were investigated and showed that cyclooctene and cyclohexene were oxidized efficiently to their corresponding epoxide with 100 and 31 % selectivity, respectively, in the presence of catalyst 2 . This catalytic system showed also excellent selectivity in the oxidation of benzyl alcohol.

Description: Two new discrete hetero-tetranuclear metallocycle complexes based on metalloligands, {[Zn 2 (NiL 1 ) 2 (H 2 O) 6 ] · 4H 2 O} n ( 1 ) and {[Ca 2 (NiL 2 ) 2 (CH 3 OH) 0.5 (H 2 O) 7 ] · CH 3 OH · 2H 2 O} n ( 2 ) were synthesized under self-assembly conditions and structurally determined. X-ray diffraction analyses revealed that the two compounds involve the discrete metallocyclic units, which serve as building blocks to further expand to three-dimensional supramolecular frameworks through second interactions such as hydrogen bonds and π ··· π stacking interactions. The central Zn II and Ca II ions of the compounds 1 and 2 are bridged by macrocyclic oxamido metalloligands fusing the metallocycle with “head-to-tail” arrangement. The metallocycles have Zn ··· Zn distances of 9.48 Å in 1 and Ca ··· Ca distances of 9.90 Å in 2 . Further, compounds 1 and 2 were investigated by thermogravimetric analysis.

Description: Black, shiny crystals of the molecular cluster compounds (Te 10 )[ M (Te X 4 )(Te X 3 )] 2 ( M / X = Rh/Cl ( 1 ), Ir/Br ( 2 )), (Te 10 )[Ru(TeI 4 )(TeI 2 )] 2 ( 3 ), (Te 10 )[ M (TeI 4 )(TeI 2 )] 2 (TeI 4 )(Te 2 I 2 ) ( M = Rh ( 4 ), Ir ( 5 )) as well as the one-dimensional cluster polymer (Te 10 I 2 )[Ir(TeI 4 )] 2 (Te 4 )I 2 ( 6 ) were synthesized by melting reactions of an electron-rich transition metal M ( M = Ru, Rh, Ir) with tellurium and Te X 4 ( X = Cl, Br, I). X-ray diffraction on single-crystals revealed that the compounds crystallize in the triclinic space group type P . 4 and 5 show [3+1]-dimensional modulations of their structures. All compounds contain binuclear complexes with central μ-η 4 :η 4 -bridging Te 10 units and terminal halogenidotellurate(II) groups. Each of the transition metal cations is in a slightly distorted octahedral coordination by six tellurium atoms; the two [ M Te 6 ] octahedra share a common edge. With the tellurium atoms acting as electron-pair donors, the 18 electron rule is fulfilled for the electrophilic M atoms. The central tricyclo [5.1.1.1 3, 5 ]-decatellurium molecule consists of two ecliptically stacked Te 4 rings, which are linked through two tellurium atoms. The symmetric or asymmetric 3c4e bonds along these almost linear bridges are in analogy to polyanionic forms of tellurium, while the tricyclic conformation is stabilized by the strong bonding to the transition-metal cations. Multi-center bonding (3c4e) is also present in the terminal square [Te +II X 4 ] 2– and the T-shaped [Te +II X 3 ] – groups. The crystal structures of 4 and 5 are organized in layers of (Te 10 )[ M (TeI 4 )(TeI 2 )] 2 n+ clusters ( n ≤ 2) that are quite robust upon oxidation or reduction as shown by molecular calculations. These clusters alternate with incommensurately modulated layers that probably consist of TeI 4 2– anions and a previously unknown Te 2 I 2 molecule. The uncertainty arises primarily from equal scattering powers of I and Te atoms as well as from the known flexibility of the electron count of the Te 10 unit. In 6 , neutral Te 4 rings concatenate (Te 10 I 2 )[Ir(TeI 4 )] 2 clusters into chains, which run parallel to the a axis.

Description: A hexanuclear metallamacrocycle complex [Ni( i Pr 3 tacn)(dca)(PF 6 )] 6 ( 1 ) was obtained by using the tridentate ligand 1, 4, 7-triisopropyl-1, 4, 7-triazacyclononane ( i Pr 3 tacn) and the flexible ligand dicyanamide (dca). The complex was characterized by X-ray crystallography and magnetic measurements. Complex 1 contains hexacyclic rings adopting chair conformation, which can be described as metallamacrocycle. Variable-temperature magnetic measurements reveal antiferromagnetic interactions across the single end-to-end dca bridges in compound 1 .

Description: The new metal-organic framework [Cd(bqdc)(phen)] n ( 1 ) (bqdc = 2, 2′-biquinoline-4, 4′-dicarboxylate, phen = 1, 10-phenanthroline) was hydrothermally synthesized by hetero-ring carboxylate ligand and N-containing auxiliary ligand. The structure of 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR spectroscopy, X-ray powder diffraction, and TG analysis. Single-crystal X-ray structural analysis shows that complex 1 is an infinite two-dimensional framework containing aesthetic meso -helix. These two-dimensional coordination networks are interconnected through aromatic π–π stacking and C–H ··· O hydrogen bonding interactions to afford a 6-connected (4 12 .6 3 ) three-dimensional supramolecular architecture. Furthermore, the photoluminescent property of complex 1 was studied.

Description: Two coordination polymers (CPs), {[Zn 2 (BMB)(5-AIPA) 2 ] · 2H 2 O} n ( 1 ) and [Zn(BMB)(5-NIPA)] n ( 2 ) {BMB = 1, 4-bis[(2-methyl-imidazol-1-yl)methyl]benzene, 5-AIPA = 5-aminoisophthalic acid, 5-NIPA = 5-nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double-layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left-handed helical chains and two types of meso -helical chains along different directions.

Description: Treatment of 3-(2-pyridyl)[1,2,3]triazolo[1, 5- a ]pyridine ( L 1 ) with [Ru II (CO)(PPh 3 ) 3 (H) 2 ] or [Ru II (DMSO) 4 (Cl) 2 ] produced the mononuclear compounds [Ru II ( L 1 )(CO)(H)(PPh 3 ) 2 ](PF 6 ) ( 1 ) and [Ru II ( L 1 ) 3 ](PF 6 ) 2 ( 2 ), respectively, which were characterized by IR, UV, CV, and 1 H NMR spectroscopy as well as ESI mass spectrometry. The crystal structure of 1 was determined by X-ray crystallography and the luminescence properties of both compounds were investigated.

Description: Few-layer graphene-like sheets of MoS 2 , WS 2 , MoSe 2 and WSe 2 were prepared by employing two methods. The first method uses microwave synthesis in ethylene glycol or water medium and the second method involves laser irradiation of the bulk samples dispersed in dimethylformamide. The few-layer dichalcogenide samples were characterized by various microscopic and spectroscopic techniques. These graphene mimics show room-temperature ferromagnetism and exchange bias besides magnetoresistance at room temperature. We have deposited nanoparticles of gold, silver, and platinum on few-layer WS 2 and characterized the nanocomposites. Nanocomposites of MoS 2 with reduced graphene oxide show increase in resistivity with increasing amount of MoS 2 . The polyaniline MoS 2 composite prepared by in situ polymerization of aniline in the presence of few-layer MoS 2 shows evidence of polaronic character.

Description: Seven complexes, [ Ln (ctpy)(NO 3 ) 2 ] n and M (ctpy) 2 · 4H 2 O [ Ln = Gd ( 1 ), Dy ( 2 ), Er ( 3 ); M = Co ( 4 ), Ni ( 5 ), Cu ( 6 ), Zn ( 7 )] with the ligand 2, 2′:6′,2′′-terpyridine-4′-carboxylic acid (Hctpy) were hydrothermally synthesized. X-ray diffractional analysis reveals that the isomorphous compounds 1 – 3 adopt one-dimensional chain-like structures, whereas 4 – 7 are isomorphic monomers. Luminescence spectroscopy measurements indicates that compound 7 exhibits photoluminescence in the solid state at room temperature.

Description: A series of new potassium and rubidium sulfido ferrates were synthesized from iron and sulfur using elemental potassium and Rb 2 S as alkali element sources. The structures of all title compounds were determined by means of single-crystal X-ray data. Isolated ortho anions [Fe III S 4 ] 5– , together with disulfide and sulfide anions, are the structure elements in K 9 [FeS 4 ](S 2 )S (monoclinic, space group P 2 1 / c , a = 1068.58(2), b = 787.480(10), c = 2372.96(3) pm, β = 102.9670(10)°, Z = 4, R 1 = 0.0325). The diferrates A 6 [Fe III 2 S 6 ], among which only the sodium and the cesium salts were known so far, contain dimers of two edge-sharing [FeS 4 ] tetrahedra. The potassium and the monoclinic form of the rubidium compound (monoclinic, space group P 2 1 / c , a = 772.50(1)/796.06(5), b = 1251.24(2)/1291.35(8), c = 1002.80(1)/1032.40(6) pm, β = 127.5260(10)/127.163(4), Z = 2, R 1 = 0.0356/0.0466) crystallize with the Cs 3 GaSe 3 structure type. The second, orthorhombic form of Rb 6 [Fe III 2 S 6 ] is isotypic to the cesium ferrate (orthorhombic, space group Cmca , a = 1884.36(3), b = 695.660(10), c = 1296.09(2) pm, Z = 4, R 1 = 0.0220) forming the Ba 3 AlSb 3 structure type. The rubidium ferrate Rb 8 [Fe 4 S 10 ] crystallizes with a new structure type (triclinic, space group P , a = 744.65(3), b = 851.21(3), c = 1042.77(4) pm, α = 77.990(2), β = 85.244(2) γ = 81.051(2)°, Z = 1, R 1 = 0.0537). The structure exhibits novel tetrameres [Fe 4 S 10 ] 8– of edge-sharing tetrahedra, which represent segments of the well-known chain compounds A [FeS 2 ]. K 7 [Fe II/III S 2 ] 5 (monoclinic, space group C 2/ c , a = 2790.1(3), b = 1153.74(13), c = 720.17(8) pm, β = 102.746(8)°, Z = 4, R 1 = 0.0407) exhibits SiS 2 analogous chains of edge-sharing [FeS 4 ] tetrahedra and contains iron in oxidation states II and III in a 2:3 ratio. This compound is an interesting “intermediate” inbetween the ferrate(III) K[Fe III S 2 ] and K 3 [Fe II/III S 2 ] 2 , with a 1:1 ratio of Fe II :Fe III .

Description: Phase Change Materials are solids which are characterized by a unique combination of properties. They exist in an amorphous and a crystalline phase with remarkably different optical and electrical properties caused by an unusual change of bonding when the amorphous phase is crystallized. It is possible to change the phase of such a material in very short times (nanoseconds) and repeatedly between the two phases which makes phase change materials ideal candidates for data storage. This paper reviews in detail the relationship between the bonding mechanisms and the resulting physical properties of phase change materials. It describes the change of bonding from ordinary covalent bonding in the amorphous phase to resonance bonding in the crystalline phase with additional disorder, resulting in unconventional physical properties of phase change materials. These properties lead to the development of phase change data storage applications. Phase change optical data storage, phase change random access memory, and emerging applications including neuromorphic computing are described with particular emphasis on material requirements and material engineering for phase change random access memory.

Description: Solid-state reactions of La 2 O 3 , LaBr 3 , and MoO 3 in molar ratios of 1:1:3 lead to single crystals of LaBrMoO 4 among a few by-products, which emerge from redox reactions of Br – with hexavalent molybdenum. To obtain the analogous cerium compound, Ce 2 O 3 was synthesized in situ by using CeO 2 and Ce in a 3:1 molar ratio. The two rare-earth metal bromide ortho -oxidomolybdates(VI) RE BrMoO 4 ( RE = La and Ce) crystallize isotypically in the monoclinic space group Pc ( a = 982 – 977 pm, b ≈ 581 pm, c = 810 – 803 pm, β ≈ 90°, Z = 4). In the crystal structure, two crystallographically unique RE 3+ cations are present, both with similar coordination environments of three plus one Br – and six O 2– anions in the shape of distorted tetracapped trigonal prisms. The two distinguishable Br – anions both display coordination spheres of three plus one RE 3+ cations each, building up distorted tetrahedra. These are fused together via four common edges to form anti -PbO-type {[Br RE $\rm^{ e }_{4/4}$ ] 2+ } layers ( e = edge-connecting) parallel to the (100) plane. Two crystallographically different oxidomolybdate(VI) units are also found in the structure, which can be best described as strands of apically vertex-shared [MoO 5 ] 4– trigonal bipyramids along [001] represented by the formula {[MoO $\rm^{ v }_{2/2}$ O $\rm^{ t }_{3/1}$ ] 2– } ( v = vertex-connecting, t = terminal). The aforementioned {[Br RE $\rm^{ e }_{4/4}$ ] 2+ } layers and the {[MoO $\rm^{ v }_{2/2}$ O $\rm^{ t }_{3/1}$ ] 2– } chains are alternately stacked along the a axis. The peculiarity of this structure is expressed by the position of the Mo 6+ cations, which are not situated in the center of the bipyramids, but reside offset in a trigonal pyramid. Since both the (Mo1) 6+ and the (Mo2) 6+ cations are located in the same partial tetrahedron, relative to the triangular plane of the trigonal bipyramid, a structure description in a non -centrosymmetric space group is immanent. Both title compounds display a twinned crystal structure with strong similarities to those of the chloride homologues RE ClMoO 4 ( RE = La – Pr) and LaClWO 4 .

Description: Polycrystalline samples and single crystals of the new metal-rich boride V 1+ x Nb 1– x IrB 2 ( x ≈ 0.1), were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-ray diffraction and EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase adopts the Mo 2 IrB 2 -type structure (space group Pnnm , no. 58) with the lattice parameters a = 7.301(7) Å, b = 9.388(9) Å and c = 3.206(5) Å. It is the first quaternary representative of Mo 2 IrB 2 -type structure. The structure contains zigzag B 4 -fragments with boron–boron distances of 1.83–1.85 Å. The electronic density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron–boron interactions are observed in the zigzag B 4 -fragment and two significantly different Ir–B interactions are observed in the new phase and the prototype Mo 2 IrB 2 .

Description: Abstract. In situ [2+3] cycloaddition reactions of milrinone [= 3-cyano-6-methyl-5-(4-pyridyl)-2-pyridone] with sodium azide in the presence of MnCl 2 · 4H 2 O, FeSO 4 · 7H 2 O, or CoCl 2 · 6H 2 O as Lewis acids, gave three new complexes {[Mn(Mitz) 2 (H 2 O) 2 ] · (H 2 O)} ( 1 ), {[Fe(Mitz) 2 (H 2 O) 2 ] · (H 2 O)} ( 2 ), and {[Co(Mitz) 2 (H 2 O) 2 ] · (H 2 O)} ( 3 ) [Mitz = 3-tetrazole-6-methyl-5-(4-pyridyl)-2-pyridone]. All the complexes were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction analysis, X-ray powder diffraction, and thermogravimetric analysis. X-ray diffraction analyses show that complexes 1 – 3 have isomorphous structures. The central metal atoms in these complexes are hexacoordinated and connected by two water molecules, two nitrogen atoms from different tetrazolyl groups, and two oxygen atoms from carbonyl functions respectively. The fluorescent emission spectrum of 1 in the solid-state at room temperature shows a maximal emission peak at 365 nm.

Description: Reaction of LnCl 3 with Na 2 (PDDA) (PDDA = phenylene-1, 2-dioxydiacetate) in a 1 to 2 mol ratio in aqueous solution yielded [Ln 2 (PDDA) 3 (H 2 O) 6 ] · 2H 2 O, structurally characterized for Ln = Ce ( 1 ), Sm ( 2 ) (redetermination), Tb ( 3 ) and Y ( 4 ) in a monoclinic C 2/ c array, a second related structural form [orthorhombic, Pbcn ] being obtained for Tb ( 5 ), Ho ( 6 ) and Er ( 7 ). The ‘domains of existence' of these two previously described forms are now extended to Ce–Dy, Y, and Eu–Er, respectively. Reaction under the same conditions for the heavier Yb 3+ ion yielded [Yb 2 (PDDA) 3 (H 2 O) 6 ] (∞|∞) · 4H 2 O ( 8 ), orthorhombic, Pbca . In the case of Ln = La the bimetallic species [NaLa(PDDA) 2 (H 2 O) 2 ] (∞|∞) · 4H 2 O ( 9 ) was obtained, while reaction of LnCl 3 with Na 2 (PDDA) in a 1 to 3 mol ratio led to the isolation of the isotypic (monoclinic, P 2 1 / c ) [NaLn(PDDA) 2 (H 2 O) 2 ] (∞|∞) · 4H 2 O) for Ln = Ce ( 10 ) and Sm ( 12 ). With the smaller Ln = Yb, the more definitively bimetallic [NaYb(PDDA) 2 (H 2 O) 2 ] (∞|∞) · 3H 2 O ( 13 ) (triclinic, P )) was obtained, the trihydrate solvation ascribed differing from that recorded (dihydrate) in a cosynchronous report.

Description: Various compounds in the (SnTe) x (Bi 2 Te 3 ) y series are explored by a number of techniques including diffractometry and physical property measurements. Through variation in the x and y integers, one is able to obtain a series of ternary compounds: SnBi 2 Te 4 , SnBi 4 Te 7 , SnBi 6 Te 10 , and Sn 2 Bi 2 Te 5 each show complex layering motifs similar to that of Bi 2 Te 3 . These compounds' increased complexity makes them of interest with respect to thermoelectric studies. The ZT values for cold-pressed annealed pellets are at room temperature 0.33 for SnBi 2 Te 4 , 0.27 for SnBi 4 Te 7 , and 0.15 for SnBi 6 Te 10 .

Description: Abstract. Two radical– Ln III –radical complexes, [ Ln (hfac) 3 (NITPh-Ph) 2 ] [ Ln = Gd ( 1 ) and Ho ( 2 ), hfac = hexafluoroacetylacetonate; and NITPh-Ph = 4′-biphenyl-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide] were synthesized and characterized by X-ray diffraction, elemental analysis, magnetic measurements, as well as IR and UV/Vis spectroscopy. X-ray crystal structure analysis revealed that the structures of both complexes are isomorphous, the central Ln III ions are coordinated by six oxygen atoms from three hfac ligand molecules and two oxygen atoms from nitronyl radicals. The temperature dependencies of the magnetic susceptibilities were studied. They showed that in the Gd III complex, ferromagnetic interactions between Gd III and the radicals and antiferromagnetic interactions between the radicals coexist in this system (with J Rad–Gd = 0.1 cm –1 , J Rad–Rad = –0.309 cm –1 ).

Description: The main objective of this paper is aimed towards a correct statistical-thermodynamic modeling and description of the effects and changes associated with the creation of different defects in the crystal structure and their connection and influence on the properties of the binary L1 2 intermetallic systems. This was done by the using of a General Defect Correlation Model (GDCM), employing applications of the Bragg-Williams-Gorsky mean-field approximation. The obtained results are compared to a model based on the Wagner-Schottky approach with application of the grand canonical ensemble for non-interacting point defects for description of the arrangement of anti-structure and vacancy defects. The basic concept includes the evaluation of such characteristics of the intermetallic materials with L1 2 structures as the virtual critical temperatures of order-disorder transformations, the pair-wise interaction and defect formation energies, thermodynamic activities and defect concentrations, and also descriptions of long-ranged (LRO) and short-ranged (SRO) atomic correlations in the crystal lattice (including the possible correlation of nearest neighbor point defect combinations), which is difficult to obtain by other methods. The model calculations also are tested using experimental data on thermodynamic and structural properties.

Description: The formation of the thioantimonates [M(tren)Sb 4 S 7 ] (M = Fe, Zn; tren = tris(2-aminoethyl)amine) has been studied with in-situ energy dispersive X-ray diffraction (EDXRD) under solvothermal conditions. Up to 60 % amine concentration the compound [Fe(tren)Sb 4 S 7 ] coexists with an unknown crystalline material until the end of the reaction. In the concentration range 70–90 % amine the unknown compound and [Fe(tren)Sb 4 S 7 ] are formed at the beginning of the reaction and when the unknown compound starts to disappear a new mixed-valent thioantimonate [Fe(tren)FeSbS 4 ] nucleates and crystallizes. Using a 100 % tren solution only [Fe(tren)FeSbS 4 ] could be identified in the powder patterns. The analysis of the data collected under real conditions clearly shows a strong correlation between the disappearance of the unknown compound and the formation of the mixed-valent thioantimonate. Evidences are presented that Fe II /Fe III redox reactions play an important role for nucleation and crystal growth of a distinct iron-containing thioantimonate. Because Zn 2+ is not redox active the formation processes are different and no crystalline intermediate could be detected.

Description: Black crystals of the rubidium uranium selenophosphate Rb 4 U 2 P 5 Se 17 have been prepared by the solid-state reaction of uranium, P 2 Se 5 , and Rb 2 Se 3 at 1023 K. The compound crystallizes with four formula units in the triclinic space group P with cell constants at 100 K of a =10.0824(2), b = 10.6905(2), c = 15.7845(3) Å, α = 84.678(1), β = 76.125(1), γ = 85.874(1)°. Its complex three-dimensional structure displays four different types of ligands that bridge uranium atoms. Three are P 2 Se 6 4– anions in different bonding modes and the fourth is an asymmetric Se 2 2– dianion. The compound may be written Rb 4 U 2 (P 2 Se 6 ) 2.5 (Se 2 ) and is charge-balanced as a U 4+ compound.

Description: Two new nickel(II) complexes, [Ni(4, 4′-bpy)(H 2 O) 4 ] n · n (cpp) · 0.5 n H 2 O ( 1 ) and [Ni(cpp)(4, 4′-bpy)(H 2 O) 2 ] n ( 2 ) [4, 4′-bpy = 4, 4′-bipyridine, H 2 cpp = 3-(4-carboxyphenyl)propionic acid] were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermal analysis. In complex 1 , Ni II ions are bridged by 4, 4′-bpy into 1D chains, and cpp ligands are not involved in the coordination, whereas in complex 2 , cpp ligands adopt a bis(monodentate) mode and link Ni II ions into 2D (4, 4) grids with the help of 4, 4′-bpy ligands. Triple interpenetration occurs, which results in the formation of a complicated 3D network. The difference in the structures of the two complexes can be attributed to the different reaction temperatures and bases.

Description: Exploiting thiacalix[4]arene and sulfur-bridged bisphenolates as ligands for bioinorganic studies involving iron(III) requires the prior development of synthetic routes (varying substituents and reaction conditions) to construct complexes with low nuclearities and accessible coordination sites, which was in the focus of this investigation. Treating p - tert -butylthiacalix[4]arene (H 4 TC) and 1, 4-dimethyl- p - tert -butylthiacalix[4]arene (Me 2 H 2 TC) with Fe[N(SiMe 3 ) 2 ] 3 yielded in the formation of the iron(III) complexes [(Me 3 SiTC) 2 Fe 2 ] ( 1 ) and [(Me 2 TC) 3 Fe 2 ] ( 3 ), respectively. While 1 is a sandwich compound, in 3 one [Me 2 TC] 2– unit is bridging two [Me 2 TCFe] + moieties. Employing thiobisphenolates as ligands it turned out, that in dependence on the residues R and the preparation method it is possible to selectively access sandwich, anionic or neutral complexes, which were shown to contain central high-spin iron(III) atoms. The syntheses, structures, and electronic properties of three iron(III) bisphenolate complexes, [ Cl L 2 Fe]NEt 3 H ( 4 ), [ Me LFeCl 2 ]NEt 3 H ( 5 ), and [ t Bu LFeCl(thf)] ( 7 ) are discussed.

Description: Microporous zeolites Na-Y and K-Y were converted into the NaNH 4 -Y and KNH 4 -Y modifications by ion exchange being active in dealumination. Removal of framework aluminium and silicon is accompanied by formation of secondary mesopores. Internal mesopores are formed in the centre of zeolite crystals and external pores at their surface. Formation of mesopores changes the sorption behaviour.Residual alkali metal cations as Na + or K + stabilise, however, the framework ≡Si-O-Al≡ bonds. Because of inhomogeneous distribution of sodium ions, in NaNH 4 -Y less internal but more external mesopores are formed. Potassium ions of KNH 4 -Y are more homogeneous distributed over the framework why a more balanced formation of secondary pores takes place.

Description: Three new lanthanide-organic coordination polymers, {[ Ln 2 (bpdc) 2 (H 2 O) 6 (NO 3 )] · NO 3 } [ Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 )] (H 2 bpdc = 2, 2′-bipyridine-6, 6′-dicarboxylic acid) were synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy as well as single-crystal and powder X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that compounds 1 – 3 are isostructural, composed of two dimensional honeycomb network linked by bpdc ligands. The magnetic property of compound 3 was investigated.

Description: . The quaternary diamond-like semiconductor, Cu 2 ZnSiS 4 , was synthesized by high-temperature solid-state synthesis at 1000 °C. High-resolution synchrotron X-ray powder diffraction of this product revealed the presence of two polymorphs. This data confirms that the known α-Cu 2 ZnSiS 4 exists with the wurtz-stannite structure in the noncentrosymmetric space group Pmn2 1 . The new polymorph, β-Cu 2 ZnSiS 4 , crystallizes in the noncentrosymmetric space group Pn with a = 6.134092(6) Å, b = 6.392752(5) Å, c = 7.421228(8) Å, β = 90.056(1)°, Z = 2, χ 2 = 5.554, R p = 0.0857 and wR p = 0.1173. Electronic structure calculations performed for both polymorphs indicate direct bandgaps of 1.3 and 1.7 eV at the Γ-point, respectively.

Description: The reaction of 1-methylimidazole and α,α-dibromo- p -xylene was followed by a metathesis reaction with fluorinated anion sources, which yielded new fluorinated imidazolium salts [C 6 H 4 (CH 2 (C 4 H 6 N 2 ) 2 ] 2+ 2[ A ] – where A = BF 4 ( 2 ), PF 6 ( 3 ), CF 3 SO 3 ( 4 ), and CF 3 COO ( 5 ). The compounds were characterized by 1 H-, 13 C-, 19 F-, 31 P NMR, and IR spectroscopy. Single crystal X-ray diffraction data of compounds 2 , 3 , and 4 were also reported, whereas compound 5 was found to be a liquid. The solid compounds crystallized in the monoclinic P 2 1 / c space group and have similar crystallographic parameters. The study revealed that the different fluorinated anions affected the spatial arrangement of atoms and the extent of cation–anion interactions, hence, influenced the stability and coordination properties of the imidazolium salts. A trend was observed which related the strength of cation–anion interaction to physical properties such as melting point.

Description: Three new 2D/3D supramolecular architectures derived from Cu-organic subunits and Keggin anions, [Cu II 2 (biz) 8 (HPMo VI 10 Mo V 2 O 40 )(H 2 O) 2 ] · 2H 2 O ( 1 ), [Cu I 4 (biz) 8 (SiW 12 O 40 )] · 2H 2 O ( 2 ) and [Cu I 2 (dmbiz) 4 (Hdmbiz) 2 (SiW 12 O 40 )] ( 3 ) (biz = benzimidazole, dmbiz = 5, 6-dimethyl benzimidazole), were obtained under hydrothermal conditions. Single crystal X-ray diffraction analysis reveals that compound 1 has two kinds of [Cu II (biz) 2 ] 2+ cations, which are further extended by Keggin anions into a 2D (4, 8)-connected supramolecular network by hydrogen bonding interactions. In compound 2 , four types of [Cu I (biz) 2 ] + subunits link the [SiW 12 O 40 ] 4– anions to form a 3D (2, 6)-connected supramolecular structure. Compound 3 shows a 3D supramolecular network with a NaCl-type topology constructed by [Cu I (dmbiz) 2 ] + subunits, anions, and discrete [Hdmbiz] + cations. Moreover, the electrochemical and photocatalytic properties of compounds 1 and 2 were investigated.

Description: The synthesis and single crystal X-ray structure of the multifunctional acrylamide-derived ligand N -triazolylpropanamide ( 1 , = NTPA) are reported. The title compound was prepared in 72 % yield by Michael addition of 1, 2, 4-triazole and acrylamide in the presence of Triton B (= trimethylbenzylammonium hydroxide) as catalyst. Treatment of 1 with FeCl 3 (H 2 O) 6 in MeOH/MeCN led to reduction and formation of the iron(II) complex (NTPA) 2 FeCl 2 (MeOH) 2 ( 2 , yellow prisms, 52 % yield). Both 1 and 2 were structurally characterized by X-ray diffraction. Surprisingly, the NTPA ligands in 2 are coordinated to iron in a monodentate fashion through a triazole ring nitrogen atom. In the crystal, both compounds form supramolecular hydrogen-bonded networks.

Description: TlCu 3 Lu 2 Se 5 and Tl 2 Cu 5 Lu 3 Se 8 were prepared by the reaction of copper and lutetium metal with elemental selenium in an excess of TlCl as flux at 850 °C. Orange TlCu 3 Lu 2 Se 5 or deep orange Tl 2 Cu 5 Lu 3 Se 8 lath-shaped crystals emerged from these reactions. TlCu 3 Lu 2 Se 5 crystallizes in the orthorhombic space group Cmcm [ a = 404.83(2), b = 1432.56(8), c = 1670.81(9) pm, Z = 4], whereas Tl 2 Cu 5 Lu 3 Se 8 crystallizes in the monoclinic space group Cm [ a = 1427.23(8), b = 404.59(2), c = 1464.37(8) pm, β = 110.52(1), Z = 2]. In both structures the Tl + cations are eightfold coordinated with Se 2– anions in the shape of a bicapped trigonal prism and the Cu + cations are fourfold coordinated with Se 2– anions in both single [CuSe 4 ] 7– and double tetrahedral [Cu 2 Se 6 ] 10– units. The latter copper-selenium units are connected to each other through edges to build corrugated {[Cu 3 Se 5 ] 7– } layers in TlCu 3 Lu 2 Se 5 and a three-dimensional {[Cu 5 Se 8 ] 11– } framework in Tl 2 Cu 5 Lu 3 Se 8 . The lutetium Lu 3+ cations are sixfold coordinated with Se 2– anions in an octahedral environment. The [LuSe 6 ] 9– polyhedra form only double octahedral chains in the first compound, while both single and double chains are found in the second. The double chains are joined to each other through vertices to form markedly corrugated {[Lu 2 Se 5 ] 4– } layers in TlCu 3 Lu 2 Se 5 . In Tl 2 Cu 5 Lu 3 Se 8 both single and double chains are connected to build less corrugated {[Lu 3 Se 8 ] 7– } layers. The two compounds are three-dimensional anionic frameworks {[Cu 3 Lu 2 Se 5 ]} – and {[Cu 5 Lu 3 Se 8 ]} 2– , respectively, in which the Tl + cations occupy channels.

Description: A novel discrete neutral Cd 17 sulfide cluster (denoted CMM-9) with seven corners has been synthesized by slow diffusion of methanol into a mixed solution (DMF/CS 2 = 1:1, weight ratio) containing an ionic starting material CMM-4. The structures of CMM-4 and CMM-9 are determined from single crystal X-ray diffraction data collected at 150 K. The structure of the new Cd 17 cluster is distinctly different from the well-known C1 cluster that also has 17 Cd sites. The UV/Vis spectrum of the new cluster CMM-9 revealed a maximum absorption at 305 nm in DMF solution, which is slightly red-shifted compared to the regular C1 cluster (C1, [Cd 17 S 4 (SPh) 28 ] 2– , with a maximum absorption at 296 nm).

Description: . The reaction of the electrophilic transition metal iridium with tellurium, indium, and bromine resulted in black, shiny crystals with the composition [Ir 2 Te 14 Br 12 ] 2 (InBr 4 ) 2 . X-ray diffraction on single-crystals revealed a triclinic structure (space group P ) that contains two crystallographically distinct, centrosymmetric clusters, (Te 10 )[Ir(TeBr 3 ) 2 ] 2 + and (Te 10 )[Ir(TeBr 4 )(TeBr 2 )] 2 + , as well as two tetrahedral InBr 4 – anions per unit cell. The center of the positively charged cluster is a Te 10 · – radical anion. This biconvex tricyclo [5.1.1.1 3, 5 ] unit consists of two angulated Te 4 rings that are linked by two almost linear μ-Te bridges. The radical causes an intense single ESR signal at g = 1.999. Molecular DFT-calculations show that the unpaired electron populates an orbital of the Te 10 -unit. Computational variation of the number of electrons causes noticeable variations in the Te–Te distances, providing strong evidence for the Te 10 · – radical. The decatellurium unit coordinates two iridium(III) cations as a bridging bis-tetradentate ligand. Two terminal bromidotellurate(II) groups complete the slightly distorted octahedral coordination of each transition metal atom. The two [IrTe 6 ] polyhedra share a common edge. The constitutions of the terminal ligands differ, including only TeBr 3 – anions in one type of clusters, but a combination of TeBr 4 2– and TeBr 2 groups in the other. The coordinating tellurium atoms of the central Te 10 · – and of the terminal groups act as electron pair donors, thereby fulfilling the 18-electron-rule for the iridium(III) cations.

Description: In order to perform real-time studies of solid-gas reactions involving light elements such as hydrogen and nitrogen, gas pressure, and gas flow cells were developed for in situ neutron powder diffraction. The gas pressure cell is based on a sapphire single crystal tube as a sample holder and provides high quality diffraction patterns with very low background up to 16.0 MPa hydrogen (deuterium) gas pressure and temperatures up to 400 °C. The gas flow cell contains a silica tube as sample container and is optimized for flowing ammonia as reaction gas. While it produces higher background owing to the silica, it allows much higher temperatures of up to 750 °C to be used. For both cells heating is realized contactless and without any contribution to the diffraction patterns by two lasers and so high-quality diffraction patterns allowing for a detailed Rietveld analysis can be collected on D20 (Institute Laue-Langevin) with a one minute time resolution. Examples are presented demonstrating the potential of the in situ gas cells, ranging from the nitridation of vanadium and iron powders with flowing ammonia, to the deuteration of palladium and the hydrogen storage material LaNi 5 .

Description: 3, 6-Bis(tetrazol-5-yl)-1, 2, 4, 5-tetrazine is a nitrogen-rich energetic compound readily prepared and a strong dibasic acid. By the reaction with energetic bases such including hydroxylamine, triaminoguanidine, hydrazine, and diaminourea, multiple ionic energetic materials were prepared and characterized for the first time. Both chemical (multinuclear NMR, Infrared, Raman, MS, etc) as well as explosive (Impact, Friction, Static sensitivities) properties are reported. The materials prepared, with the exception of the silver salt, which is a primary explosive, fall into the classification of low-sensitivity energetic materials due to desensitizing hydration waters. Calculated explosive performances using the EXPLO5 computer code are also reported.

Description: Hydrothermal reaction of the metalloligand {[Co(Pzdc) 2 ] · 2H 2 O} n ( 1 ) with Ce(NO 3 ) 3 · 6H 2 O yields a heterometallic 3d-4f coordination compound {[Ce 2 Co(Pzdc) 4 (H 2 O) 6 ] · 2H 2 O} n ( 2 ) (H 2 Pzdc = pyrazine 2, 3-dicarboxylic acid). X-ray structure determination, IR spectroscopy, elemental analysis, thermogravimetric analysis, and magnetic property for the targets are presented. Compound 1 affords one-dimensional double zigzag chains. Compound 2 features a three-dimensional Co II –Ce III herringbone structure, in which the slightly deformational 1 and central Ce III atoms are linked by Pzdc 2– spacers, and is further analyzed with {4.6 2 } 2 {4 2 .6 2 .8 2 }{6 3 } 2 {6 5 .8} 2 topology symbol. Magnetic property analysis reveals that the antiferromagnetic interactions occur in compound 2 due to a long-range superexchange pathway between adjacent magnetic centers. In addition, the solid state photoluminescence of 2 was investigated.

Description: The reaction of the NHC i Pr 2 Im [NHC=N-heterocyclic carbene, i Pr 2 Im = 1, 3-bis( iso propyl)imidazolin-2-ylidene] with freshly prepared NiBr 2 in thf or dme results in the formation of the air stable nickel(II) complex trans -[Ni( i Pr 2 Im) 2 Br 2 ] ( 2 ). Complex 2 was structurally characterized. Thermal analysis (DTA/TG) reveals a very high decomposition temperature of 298 °C. Reduction of 2 with sodium or C 8 K in the presence of the olefins COD (cyclooctadiene) or COE (cyclooctene) affords the highly reactive compounds [Ni 2 ( i Pr 2 Im) 4 (COD)] ( 1 ) and [Ni( i Pr 2 Im) 2 (COE)] ( 4 ). Alkylation of 2 with organolithiums leads to the formation of trans -[Ni( i Pr 2 Im) 2 ( R ) 2 ] [ R = Me ( 5 ), CH 2 SiMe 3 ( 6 )], whereas the reaction of 2 with LiCp* [Cp* = (η 5 -C 5 (CH 3 ) 5 )] at 80 °C causes the loss of one NHC ligand and affords [(η 5 -C 5 (CH 3 ) 5 )Ni( i Pr 2 Im)Br] ( 7 ).

Description: The reaction of Ph 3 SnCl, (R 4 N) 2 [Mo 6 O 19 ] and (R 4 N)OH in a molar ratio of 6:1:10 leads to the formation of (R 4 N)[(Ph 3 Sn)MoO 4 ] (R = n Pr ( 1 ), n Bu ( 2 )). Compounds 1· CH 3 CN and 2 have been charactarized by IR spectroscopy and single crystal X-ray diffraction. 1· CH 3 CN forms orthorhombic crystals, space group P 2 1 2 1 2 1 with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P 2 1 with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R 4 N + cations and polymeric [(Ph 3 Sn)MoO 4 ] – chains with an alternating arrangement of Ph 3 Sn + and MoO 4 2– groups. Treatment of (Ph 3 Sn) 2 MoO 4 with bis(ethylenediamine)copper(II) succinate yields [Cu(en) 2 (Ph 3 Sn) 2 (MoO 4 ) 2 ] ( 3 ). The zinc derivative [Zn(en) 2 (Ph 3 Sn) 2 (MoO 4 ) 2 ] ( 4 ) is obtained similarly by reaction of (Ph 3 Sn) 2 MoO 4 with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P 2 1 / n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric [(Ph 3 Sn)MoO 4 ] – chains are observed. The [M(en) 2 ] 2+ units (M = Cu, Zn) act as linkers between the [(Ph 3 Sn)MoO 4 ] – chains to give 2D layer structures with (6, 3) net topology.

Description: The reaction of the di-lithiated oxamide of 1 with two equivalents of SnCl 2 provided the tin trans -oxamide 3 . In solution, spectroscopic analysis suggests exclusively the formation of a trans -oxamide ( trans - 3 ). However, the solid state shows an atypical cis -oxamide ( cis - 3 ), where the oxamide fragment acts as an anti-Janus head ligand. An 119 Sn-NMR variable temperature experiment ([D 8 ]THF) of the trans -oxamide ( trans - 3 ) was performed however, at lower temperature no additional signal was observed, which confirmed the absence of a dynamic equilibrium. Dispersion-corrected density functional calculations revealed that the cis conformation of this tin(II) oxamide complex is more stable than the trans isomer by 1.4 kcal · mol –1 .

Description: To explore the coordination abilities of nitronyl nitroxide ligands, two ligands substituted with quinoxaline ( L 1 ) and 2-phenyl-1, 2, 3-triazole ( L 2 ) and their Ni II and Zn II complexes: Ni( L 1 )(hfac) 2 ( 1 ), Ni( L 2 )(hfac) 2 ( 2 ), and Zn( L 2 )(hfac) 2 ( 3 ) (hfac = hexafluoroacetylacetonate), were synthesized and characterized. X-ray single-crystal diffraction analysis shows that compound 1 has a mononuclear structure, which is further linked into a three-dimensional (3D) supramolecular network by C–H ··· F hydrogen-bonding, C–H ··· π, and π ··· π stacking interactions. Complexes 2 and 3 have similar mononuclear structures, which are further linked into one-dimensional (1D) supramolecular chains by various intermolecular weak interactions, such as C–H ··· F hydrogen-bonding, and π ··· π stacking interactions. The results indicate that the steric bulk of L 1 and L 2 and the existence of hexafluoroacetylacetonate (hfac) play important roles in controlling the formation of the final frameworks of complexes 1 – 3 . Moreover, the luminescent properties of the ligands and their complexes were investigated in detail.

Description: Greenish gray microcrystalline powders of Ba 3 [Ir(CN) 3 ] were prepared from pressed pellets of mixtures of Ba 2 N, iridium, NaCN, and graphite at 1020 K under inert conditions. Neutron diffraction data at 293 K revealed the crystal structure of the Ir compound ( P 6 3 / m (no. 176), a = 9.2277(8) Å, c = 5.7878(6) Å) to be isostructural to Sr 3 [Co(CN) 3 ] and Ba 3 [Co(CN) 3 ]. The trigonal-planar complex [Ir 3 (CN) 3 ] 6– is surrounded by nine Ba 2+ ions forming a tricapped trigonal prism. Elongated C–N distances and low vibrational frequencies in the highly reduced iridium complex are similar to those observed in the corresponding cobalt compounds.

Description: Abstract. The self-assembly of glycyl- L -leucine, Cu(NO 3 ) 2 · 3H 2 O and 4, 4′-bipyridine resulted in the tetranuclear-based metal-dipeptide supramolecular framework [Cu 4 (C 8 H 14 N 2 O 3 ) 4 (H 2 O) 2 (C 10 H 8 N 2 ) 2 ] · (C 10 H 8 N 2 ) · 13H 2 O ( 1 ). In the structure, the 4, 4′-bipyridine-bridged tetranuclear complex of Cu II -glycyl- L -leucine interacts with each other to form a 1D hydrogen-bonded chain including uncoordinated 4, 4′-bipyridine and an interesting water chain in different channels. Under similar reaction conditions, racemic glycyl- D , L -leucine gave rise to the centrosymmetric dinuclear complex [Cu 2 (C 8 H 14 N 2 O 3 ) 2 (C 10 H 8 N 2 )] · 2H 2 O ( 2 ), which is linked into a 2D hydrogen-bonded structure without 4, 4′-bipyridine included.

Description: Pigeon blood red powder samples of SnO were synthesized via a soft chemistry route. A precipitate was obtained from a freshly prepared SnCl 2 solution containing phosphorus acid by adding ammonia until a pH value of 4.9 is reached. Heating of the mixture at 95 °C leads after 5 d to microcrystalline powders of red SnO. The crystal structure was solved and refined from X-ray powder diffraction data ( Cmc 2 1 ; a = 5.0045(3) Å, b = 5.7457(3) Å, c = 11.0485(5) Å, Z = 8). Red SnO crystallizes in a new structure type. Characteristic building units are double layers of tin and oxygen atoms. The tin atoms are surrounded by four oxygen atoms with distances ranging from 2.04 Å to 2.67 Å, and the highly asymmetric coordination around the Sn 2+ ions indicates the presence of a stereochemically active lone pair. LMTO band structure calculations show that the red modification of SnO is an insulator. The electronic structures of red SnO and the zero band gap semiconductor black SnO are compared. The lone pairs of the tin atoms are visualized via the electron localization function.

Description: . The nitridogallate Ca 2 Ga 3 MgN 5 was obtained from reaction of the elements in sodium flux with Na-azide at 760 °C in weld shut niobium ampoules. Crystal structure solution and refinement was carried out on the basis of single-crystal X-ray diffraction data. Ca 2 Ga 3 MgN 5 [space group C 2/ m (no. 12), a = 11.160(2), b = 3.2965(7), c = 8.006(2) Å, and β = 109.93(3)°, Z = 2] shows an anionic substructure made up of mixed (Mg/Ga)N 4 tetrahedra, which are sharing both common vertices and edges building a three-dimensional network. The crystal structure of Ca 2 Ga 3 MgN 5 is related to known alkaline earth nitridosilicates ( M II 2 Si 5 N 8 , M II = Sr, Ba), but is significantly higher condensed due to additional edge-sharing in the anionic substructure.

Description: The X-ray structures of 4-amidiniumpyridine acetate, ( 1· H)AcO, and of cis -[Pt( 1 ) 2 (PPh 3 ) 2 ](NO 3 ) 2 ( 2 ), as well as their IR spectra, reveal intramolecular hydrogen bonding, which held together the cations and the anions. The IR spectroscopic data suggest that this may be so also in cis -[PtCl( 1 )(PPh 3 ) 2 ](BF 4 ) ( 3 ). In ( 1· H)AcO and in 2 extensive intermolecular hydrogen bonding networks span through the whole crystals.

Description: An earlier reported series of the [ Ln (Ur) 4 (H 2 O) 4 ]I 3 ( Ln = Y, La, Nd, Eu, Gd, Dy, Ho, Er; Ur = urea) complexes was completed with seven new compounds ( Ln = Ce, Pr, Sm, Tb, Tm, Yb, Lu); one of them, [Ce(Ur) 4 (H 2 O) 4 ]I 3 , was studied by X-ray diffraction. The most striking feature of the [ Ln (Ur) 4 (H 2 O) 4 ]I 3 structures is the presence of two types of coordinated urea molecules. There are two planar symmetric and two non-planar asymmetric urea molecules. The Ln –O–C bond angles vary in the ranges 163.06–165.71° and 148.42–152.42° for symmetric and asymmetric urea ligands, respectively, correlating with the ionic mode of urea coordination. To elucidate the role of aqua ligands for the urea coordination mode, two water-free perchlorate complexes, [La(Ur) 8 ](ClO 4 ) 3 · 2Ur and [La(Ur) 7 (OClO 3 )](ClO 4 ) 2 were synthesized and structurally characterized. In these complexes, all urea molecules are planar symmetric; however, both covalent and ionic types of urea coordination with the La–O–C bond angles varying in the 132.4–142.3° and 145.5–159.1° ranges, respectively can be observed.

Description: Contact with SO 2 causes almost immediate dissolution of tetraalkylammonium halides, R 4 N X , ( R = CH 3 (Me), X = I; R = C 2 H 5 (Et), X = Cl, Br, I; R = C 4 H 9 ( n Bu), X = Cl, Br), with the formation of an adduct, [ R 4 N] + [(SO 2 ) n X ] ( n = 1–4). Vapor pressure measurements indicate the proclivity for SO 2 uptake follows the order N(CH 3 ) 4 + 〈 N(C 2 H 5 ) 4 + 〈 N(C 4 H 9 ) 4 + . This trend is in accord with the Jenkins–Passmore volume-based thermodynamic model. Born–Haber cycles, incorporating the lattice energy and gas phase energy terms, are used to evaluate the energetic feasibility of reactions. Density functional theory calculations (B3PW91; 6-311+G(3df)) have been used to calculate the energetics of (SO 2 ) n X – ( X = Cl and Br) anions in the gas phase. The experimental studies show that tetraalkylammonium halides are feasible sorbents for SO 2 . In order to correlate the theoretical model, experimental enthalpy, Δ r H° and entropy, Δ r S° changes have been determined by the van't Hoff method for the binding of one SO 2 molecule to (C 2 H 5 ) 4 NCl, resulting in the liquid adduct (C 2 H 5 ) 4 NCl · SO 2 . The structure of the analogous 1:1 bromide adduct, (C 2 H 5 ) 4 NBr · SO 2 , has been determined by single-crystal X-ray diffraction (monoclinic, P 2 1 / c , a = 9.1409(14) Å, b = 12.3790(19) Å, c = 11.3851(17) Å, β = 107.952(2)°, V = 1225.6(3) Å 3 ). The structure consists of discrete alkylammonium cations, bromide anions and SO 2 molecules with short contacts between the anion and SO 2 molecules. The (C 2 H 5 ) 4 N + cationadopts a transoid conformation with D 2 d symmetry, and represents a rare example of a well-ordered (C 2 H 5 ) 4 N + cation in a crystal structure. The Br – anions and SO 2 molecules forms a chain, (SO 2 Br – ) n , with bifurcated contacts. Non-bonding electron pairs on the halide anions engage in electrostatic interactions with the sulfur atoms and charge-transfer interactions with the antibonding S–O orbitals of the bound SO 2 moiety. Raman and 17 O NMR spectra provide compelling evidence for a charge-transfer interaction between SO 2 molecules and the halide ions.

Description: The reaction of 1-naphthylamine with two equivalents of chlorodiphenylphosphine in the presence of triethylamine gave the ligand C 10 H 7 -1-N(PPh 2 ) 2 ( 1 ). Reaction of 1 with PdCl 2 (CH 3 CN) 2 or PtCl 2 (cod) (1:1 molar ratio) afforded the complexes cis -[PdCl 2 {C 10 H 7 -1-N(PPh 2 ) 2 }] ( 2 ) and cis -[PtCl 2 {C 10 H 7 -1-N(PPh 2 ) 2 }] ( 3 ), respectively. Compounds 1 – 3 were identified and characterized by multinuclear NMR ( 1 H, 13 C, 31 P NMR) and IR spectroscopy. Crystal structure determinations of complexes 2 and 3 were carried out.

Description: In the course of investigations relating to magnesia cement the basic magnesium salt hydrates 2Mg(OH) 2 · MgCl 2 · 2H 2 O (2-1-2 phase) and 2Mg(OH) 2 · MgCl 2 · 4H 2 O (2-1-4 phase) were found as stable phases in the system MgO-MgCl 2 -H 2 O at a temperature of T = 120 °C and were characterized by thermal analysis, Raman spectroscopy and X-ray powder diffraction. The crystal structures of the 2-1-2 and 2-1-4 phases were determined from high resolution laboratory X-ray powder diffraction data.Both phases crystallize in space group C 2/ m with Z = 2 (2-1-2: a = 15.3285(3) Å, b = 3.2208(5) Å, c = 8.1096(2) Å, β = 91.99(1)°, V = 400.13(2) Å 3 ; 2-1-4: a = 15.1264 Å, b = 3.1715(2) Å, c = 10.5230(1) Å, β = 101.55(1)°, V = 494.60(1) Å 3 ). The main building unit of both crystal structures is made up by infinite triple chains of edge-linked distorted MgO 6 octahedra. In case of the 2-1-4 phase, the parallel stacks are in addition separated by interstitial one dimensional zig-zag chains of disordered Cl – ions and H 2 O molecules.

Description: Two complexes, namely [Mn 3 (hpda) 2 (H 2 O) 8 ] n ( 1 ) and [Co 3 (hpdaH) 3 (H 2 O) 7 ] · (4, 4′py) · (H 2 O) 3 ( 2 ) (hpdaH 3 = 4-hydroxypyridine-2, 6-dicarboxylic acid) were synthesized under hydrothermal conditions and were characterized by elemental analysis, IR spectrocopy, and X-ray diffraction. Complex 1 forms a 1D linear chain, which is extended by hydrogen bonds resulting in a 3D network. Complex 2 consists of a trinuclear cobalt(II) unit, which is further linked by hydrogen bonds to form a 3D supramolecular network. Magnetic measurements show that there is a weak antiferromagnetic interaction between the adjacent Mn II ions in 1 .

Description: Two different systems were used for syntheses of metal selenides, [Mn(en) 3 ][In 2 Se 5 ] ( 1 ) and [MnSe(en) 0.5 ] ( 2 ) by the reactions of In 2 Se 3 , MnCl 2 , and selenium powder at 170 °C for 6 days. Compound 1 contains a one-dimensional [In 2 Se 5 ] 2– chain propagating along the crystallographic c axis separated by [Mn(en) 3 ] 2+ complex cations. The anionic chain is constructed by vertex-linked InSe 4 tetrahedra linked by Se–Se bridges and contains four-membered [In 2 Se 2 ] rings and five-membered [(In 3+ ) 2 (Se 2 2– )(Se 2– )] rings. Compound 2 has a three-dimensional network containing a monolayer of [MnSe] slabs, which is interconnected by bridging en linkers. The [MnSe] slab is a puckered 6 3 (honeycomb) net formed by alternating three-coordinate manganese and selenium atoms.

Description: A chiral helical coordination polymer [Ag(pmta)] n ( 1 ) was prepared by the reaction of the asymmetric organic spacer 2-pyrimidylthioacetic acid (Hpmta) with silver(I) acetate. Complex 1 has a hetero-chiral coaxial helical structure, which is further extended into a 2D network structure by various supramolecular interactions. Furthermore, complex 1 exhibits strong fluorescence emission in the solid state and modest power second-harmonic-generation (SHG) efficiency at room temperature.

Description: Nanoparticles of a three-dimensional coordination polymer, [Ag(μ 4 -4-ABS)] n ( 1 ) [4-ABS – = 4-aminobenzenesulfonate], were synthesized by thermal treatment with oleic acid at 523 K from a well-ground powder of its single crystals. The single-crystal X-ray data of compound 1 shows the formation of a 3D silver(I) coordination polymer with a disordered tetrahedral coordination sphere around the Ag I ions. The structure of compound 1 differs strongly from the coordination polymer, [Ag(μ 5 -TS)] n ( 2 ) [TS – = toluene-4-sulfonate], which was reported previously. The coordination number of Ag I ions in compound 1 is four, with no Ag ··· C interactions, which is also in contrast to compound 2 . AgBr nanoparticles were fabricated by using the reverse micelles technique. These nanoparticles were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of compound 1 single crystal was studied by thermogravimetry (TG) and differential thermal analysis (DTA).

Description: Two new Ag I compounds, [Ag(MA)(FA) 0.5 ] n ( 1 ) and [Ag(MA)(PES)] n · n (MA) · n (H 2 O) ( 2 ), were prepared by slow solvent evaporation methods from mixtures of MA and AgNO 3 in the presence of FA or PES co-ligand [MA = melamine, FA = fumaric acetate and PES = 2-(4-pyridyl)ethanesulfonate]. Single crystal X-ray analysis reveals that 1 features a two-dimensional undulated layer framework that is further assembled into a three-dimensional interdigitated framework directed by hydrogen bonds. Compound 2 features a zero-dimensional dinuclear structure linked by weak Ag ··· O interactions, which is further extended into a complicated three-dimensional supramolecular framework constructed by hydrogen bonds.

Description: A new coordination polymer [Co(Htci)(bpe) 0.5 ] · H 2 O ( 1 ) [bpe = 1, 2-bis(4-pyridyl)ethylene, H 3 tci = tris(2-carboxyethyl)isocyanurate] was synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction, which reveals that 1 is a 3D pillar-layered structure.

Description: A 3D coordination polymer [Cd 3 (btrc) 2 (L1) 2 ] n ( 1 ) [H 3 btrc = 1, 2, 4-benzenetricarboxylic acid; L1 = 1, 4-bis(1-imidazolyl)butane] was synthesized under hydrothermal conditions. Single crystal X-ray diffraction study revealed that polymer 1 presents an unusual example of a trinodal (4, 6)-connected net with (4 4 · 6 2 )(4 4 · 6 10 · 8) fsc topology. In addition, this polymer was investigated by IR and luminescence spectroscopy, as well as thermogravimetric analyses.

Description: Contact with SO 2 causes almost immediate dissolution of tetraalkylammonium halides, R 4 N X , ( R = CH 3 (Me), X = I; R = C 2 H 5 (Et), X = Cl, Br, I; R = C 4 H 9 ( n Bu), X = Cl, Br), with the formation of an adduct, [ R 4 N] + [(SO 2 ) n X ] ( n = 1–4). Vapor pressure measurements indicate the proclivity for SO 2 uptake follows the order N(CH 3 ) 4 + 〈 N(C 2 H 5 ) 4 + 〈 N(C 4 H 9 ) 4 + . This trend is in accord with the Jenkins–Passmore volume-based thermodynamic model. Born–Haber cycles, incorporating the lattice energy and gas phase energy terms, are used to evaluate the energetic feasibility of reactions. Density functional theory calculations (B3PW91; 6-311+G(3df)) have been used to calculate the energetics of (SO 2 ) n X – ( X = Cl and Br) anions in the gas phase. The experimental studies show that tetraalkylammonium halides are feasible sorbents for SO 2 . In order to correlate the theoretical model, experimental enthalpy, Δ r H° and entropy, Δ r S° changes have been determined by the van't Hoff method for the binding of one SO 2 molecule to (C 2 H 5 ) 4 NCl, resulting in the liquid adduct (C 2 H 5 ) 4 NCl · SO 2 . The structure of the analogous 1:1 bromide adduct, (C 2 H 5 ) 4 NBr · SO 2 , has been determined by single-crystal X-ray diffraction (monoclinic, P 2 1 / c , a = 9.1409(14) Å, b = 12.3790(19) Å, c = 11.3851(17) Å, β = 107.952(2)°, V = 1225.6(3) Å 3 ). The structure consists of discrete alkylammonium cations, bromide anions and SO 2 molecules with short contacts between the anion and SO 2 molecules. The (C 2 H 5 ) 4 N + cationadopts a transoid conformation with D 2 d symmetry, and represents a rare example of a well-ordered (C 2 H 5 ) 4 N + cation in a crystal structure. The Br – anions and SO 2 molecules forms a chain, (SO 2 Br – ) n , with bifurcated contacts. Non-bonding electron pairs on the halide anions engage in electrostatic interactions with the sulfur atoms and charge-transfer interactions with the antibonding S–O orbitals of the bound SO 2 moiety. Raman and 17 O NMR spectra provide compelling evidence for a charge-transfer interaction between SO 2 molecules and the halide ions.

Description: A rigid imidazolate/sulfonate functionalized ligand, 6-(4-sulfonatopheny)imidazo[4, 5-f]isoindole-5, 7-dione (SPID) was designed and used for assembling reactions with Mn 2+ and Cu 2+ ions. Two 2D frameworks compounds, [Mn(H -1 SPID) 2 (DMAC) 2 ] ( 1 ) and [Cu(H -2 SPID)(H 2 O) 2 ] · 0.7DMAC · 0.3H 2 O ( 2 ) (DMAC = N , N -dimethylacetamide) were obtained. Single crystal X-ray analyses show that 1 has a 2D (4, 4)-net based on 4-connected Mn 2+ nodes and μ 2 -coordinated H -1 SPID spacers, whereas compound 2 has a 2D (6, 3)-net built of 3-connected Cu 2+ nodes and μ 3 -coordinated H -2 SPID spacers. Additionally, the thermal behavior of 1 and 2 is presented.

Description: A coordination polymer [Ba 12 (btc) 8 (H 2 O) 23 ] ( 1 ) was obtained by self-assembly of the corresponding metal carbonate with benzene-1, 2, 3-tricarboxylic acid ligand (H 3 btc), and its structure was determined by single-crystal X-ray diffraction studies. The results revealed that complex 1 has a three dimensional structure. In 1 , the btc 3– anions adopt four different conformation and coordination modes. Bridging btc 3– anions and μ 2 -bridging water molecules connect Ba II ions to generate a two dimensional layer. Further, μ 2 -bridging coordinated water molecules connect the Ba II ions of neighboring layers to form a three dimensional structure. Additionally, the luminescent property and thermal stability of 1 were investigated.

Description: Two novel isopropylamine-templated uranyl chromates, [(CH 3 ) 2 CHNH 3 ] 3 [(UO 2 ) 3 (CrO 4 ) 2 O(OH) 3 ] ( 1 ) and [(CH 3 ) 2 CHNH 3 ] 2 [(UO 2 ) 2 (CrO 4 ) 3 (H 2 O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X-ray diffraction crystal structure analysis [ 1 : trigonal, P 31 m , a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) Å 3 ; 2 : monoclinic, P 2 1 / c , a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) Å 3 ]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO 4 tetrahedra to form [(UO 2 ) 3 (CrO 4 ) 2 O(OH) 3 ] 3– layers, whereas, in the structure of 2 , UO 7 and UO 6 (H 2 O) pentagonal bipyramids are linked through CrO 4 tetrahedra into the [(UO 2 ) 2 (CrO 4 ) 3 (H 2 O)] 2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.

Description: The far and mid infrared (FIR/MIR) spectra of powdered Os(η 5 -C 5 Me 5 ) 2 (OsCp* 2 ) as well as the polarized Raman spectra of an oriented single crystal (where the two molecules of D 5 h symmetry in the unit cell are uniformly oriented) have been recorded. The latter allow the assignment of the observed Raman lines to irreducible representations (irreps) which agree well with the predictions of a calculation applying density functional theory. This finding suggests additional correlation of the observed (unpolarized) bands in the FIR/MIR spectra with the calculated wavenumbers (and their irreps) of IR active normal modes. Neglecting νCH vibrations an r.m.s. deviation of 15.8 cm –1 for 40 assignments (Raman and IR) could be achieved. Skeletal and intra-ligand vibrations could be identified and a number of previous assignments of the latter had to be revised. Because of mixing with skeletal modes some of the low frequency intra-ligand vibrations display a noticeable dependence on the mass of the central atom which prevents the direct transfer of the identified γCCH 3 and βCCH 3 normal modes from M Cp* 2 ( M = Fe, Ru, Os) to Ln Cp* 3 ( Ln = La, Ce, Pr, Nd, Sm) complexes.

Description: Two new polymeric iodoargentate hybrids induced by rare earth metal complexes and conjugated organic cations, {[Er(DMF) 8 ][Ag 6 I 9 ]} n ( 1 ) and [(MMP)(AgI 2 )] n ( 2 ) (MMP = 1-methyl-4-methylpyridinium) were obtained by the routine synthetic reaction and structurally determined. In compound 1 , a (Ag 6 I 9 ) n 3 n – chain is defined by edge-sharing Ag 6 I 12 units, and in 2 , the (Ag 2 I 4 ) n 2– chains are constructed by edge-sharing AgI 4 tetrahedra. C–H ··· I hydrogen bonds between cations and iodoargentate polyanions contribute to their structural extension from 1D to a 2D layer (for 1 ) and a 3D network (for 2 ). The UV/Vis spectra indicate that compared with 2 , compound 1 exhibits a narrower adsorption scope with an onset at about 360 nm, and it has a much wider bandgap of about 3.50 eV.

Description: The metal-directed self-assembly of biphenylantimony trichloride and homocarboxylic acids LH [L = 2-CHO-C 6 H 4 COO – ( 1 ), 2, 3-2F-C 6 H 4 COO – ( 2 ), 4-CF 3 –C 6 H 4 COO – ( 3 )] provided three novel tetranuclear organoantimony(V) complexes, which were characterized by elemental analysis, FT-IR, 1 H, and 13 C NMR spectroscopy as well as melting point, and X-ray single crystal analysis. In the molecular structure, four hexacoordinate antimony atoms are linked into a [Sb 2 (μ-O) 2 ] 2 (μ-O) 2 “cage” architecture by oxo-bridges which are terminally bridged by two carboxyl groups.

Description: During attempts to synthesize lanthanoid(III) fluoride oxoselenates(IV) with the simple composition M F[SeO 3 ], not only Pr 3 F[SeO 3 ] 4 , but also Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 appeared as pale green crystalline by-products in the case of praseodymium. Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 crystallizes triclinically in space group P (no. 2) with a = 701.14(5), b = 982.68(7), c = 1286.79(9) pm, α = 70.552(3), β = 76.904(3), γ = 69.417(3)° and Z = 2. The five crystallographically different Pr 3+ cations on the general positions 2 i show coordination numbers of eight and nine. [(Pr1)O 8 ] 13– and [(Pr2)O 8 ] 13– polyhedra are connected to {[(Pr1, 2) 2 O 12 ] 18– } chains along the [100] direction. [(Pr3)O 7 F] 12– , [(Pr4)O 8 F] 14– and [(Pr4)O 8 F] 14– polyhedra generate [F(Pr3, 4, 5) 3 O 19 ] 30– units about their central F – anion in triangular Pr 3+ coordination. These units form {[F(Pr3, 4, 5) 3 O 16 ] 24– } strands, again running parallel to [100]. Their alternating connection with the {[(Pr1, 2) 2 O 12 ] 18– } chains results in {[Pr 5 O 20 F] 26– } sheets parallel to the (001) plane. Like in the already known related compound Er 3 F[SiO 4 ][SeO 3 ] 2 , a three-dimensional network {[Pr 5 O 17 F] 20– } is achieved without the contribution of both the tetravalent silicon and selenium components. However, two Si 4+ and three Se 4+ cations forming tetrahedral [SiO 4 ] 4– and ψ 1 -tetrahedral [SeO 3 ] 2– units with all O 2– anions guarantee the charge balance. The formation of Pr 5 F[SiO 4 ] 2 [SeO 3 ] 3 was observed when praseodymium sesquioxide (Pr 2 O 3 : in-situ produced from Pr and Pr 6 O 11 in a molar ratio of 3 / 11 : 4 / 11 ),praseodymium trifluoride (PrF 3 ) and selenium dioxide (SeO 2 ) in 1:1:3 molar ratios were reacted with CsBr as fluxing agent for five days at 750 °C in evacuated fused silica (SiO 2 ) ampoules.

Description: Single crystals of Sr[B(C 6 H 5 O 7 ) 2 ](H 2 O) 4 · 3H 2 O, a new borate-citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C 6 H 5 O 7 ) 2 ](H 2 O) 4 · 3H 2 O was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P 2 1 / c , with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO 8 dodecahedra, BO 4 tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis.

Description: A series of [Mn 6 O 2 ( R 1 OH) 4 (sao) 6 ( R 2 COO) 2 ] complexes with terminal functional groups ( 1 : R 1 = CH 3 , R 2 = HO-C 6 H 4 , 2 : R 1 = C 2 H 5 , R 2 = H 2 N-C 6 H 4 , 3 : R 1 = CH 3 , R 2 = Cl-C 6 H 4 , 4 : R 1 = CH 3 , R 2 = CH 3 S-C 6 H 4 , 5 : R 1 = CH 3 , R 2 = I-C 6 H 4 , 6 : R 1 = CH 3 , R 2 = pymSCH 2 , 7 : R 1 = CH 3 , R 2 = ortho -pyr-SCH 3 , 8 : R 1 = C 2 H 5 , R 2 = (CH 3 ) 3 OOCNHCH 2 C 6 H 4 ; sao = doubly deprotonated salicylaldoxime ligand, pym = pyrimidyl, pyr = pyridyl) have been obtained in a reaction of a ligand R 2 C 6 H 4 COOH, salicylaldoxime, manganese(II) perchlorate and [NEt 4 ](OH) in methanol or a 1:1 mixture of ethanol and dichloromethane. In this report, structural aspects as well as preliminary studies of magnetic and thermal properties are presented. Compounds 1 , 3 , 6 , 8 exhibit an antiferromagnetic coupling of the Mn 2+ ions, whereas 4 and 7 show ferromagnetic interactions. The title compounds may act as starting materials for further derivatization addressing the functional groups.

Description: The synthesis of two new diphosphonic acid ligands, [ethane-1, 2-diylbis(azanediyl)]bis[(4-chlorophenyl)methylene]diphosphonic acid (L 1 P), [ethane-1, 2-diylbis(azanediyl)]bis[(4-bromophenyl)methylene]diphosphonic acid (L 2 P), and their corresponding copper complexes, Cu 2 (L 1 P) 2 ( 1 ) and Cu 2 (L 2 P) 2 ( 2 ) are described herein. Complex 2 was structurally characterized with X-ray single crystal diffraction. The structure of 2 consists of five-coordinate copper(II) ions with a distorted square pyramidal arrangement doubly bridged by OPO from phosphonate groups. The Cu–Cu distance is 4.7810(2) Å. The crystal packing is determined by interdinuclear hydrogen bonds, which lead to one-dimensional chains. The results of thermogravimetric investigations (TG-DTA), UV/Vis diffuse reflectance, infrared and ( 1 H and 13 C) NMR spectroscopy, as well as elemental analyses of compounds 1 and 2 are also presented.

Description: Reaction of 2, 4, 6-tri- tert -butylphenol ( 1 ) with di- n -butylmagnesium in the molar ratio 1:1 allows the synthesis of {( n Bu)Mg( μ -O R ) 2 Mg( n Bu)} ( 2 ) ( R = 2, 4, 6- t Bu 3 C 6 H 2 ), which reacts with excess 1 to give the homoleptic alcoholate complex {( R O)Mg(μ-O R ) 2 Mg(O R )} ( 3 ) ( R = 2, 4, 6- t Bu 3 C 6 H 2 ). The structures of 2 and 3 were determined by X-ray crystallography.

Description: The antimony aminoalkoxide and aminothiolates Sb( E CH 2 CH 2 NMe 2 ) 3 [ E = O ( 1 ), S ( 2 )] were synthesized and their ability to form adducts with other metal moieties investigated. Compound 1 forms 1:1 adducts with NiI 2 ( 3 ) and M (acac) 2 [ M = Cd ( 4 ), Ni ( 5 )], while 2 undergoes ligand exchange with AlMe 3 to afford Me 2 AlSCH 2 CH 2 NMe 2 ( 6 ). The structures of 2 – 4 and 6 were determined. Compound 2 incorporates three S, N -chelating ligands though the interaction with nitrogen is weaker than in analogous alkoxide complexes. Product 3 reveals one iodine has migrated from nickel to antimony, and all three alkoxide ligands bridge the two metals through μ 2 -O atoms. In contrast, in 4 , only one alkoxide links the antimony and cadmium. Compound 6 adopts the same structure, a chelating S , N ligand generating a tetrahedral center at aluminum, as known t Bu 2 AlSCH 2 CH 2 N R 2 species ( R = Me, Et).

Description: The reaction of (NH 4 ) 2 PbCl 6 and fuming sulfuric acid (65 % SO 3 ) in a sealed glass tube at 250 °C led to colorless single crystals of Pb[S 3 O 10 ] (orthorhombic, Pbcn , Z = 4, a = 10.9908(4), b = 8.5549(3), c = 8.0130(3) Å, V = 753.42(5) Å 3 ). The compound shows a three-dimensional linkage of the tenfold oxygen coordinated Pb 2+ ions and exhibits the unusual trisulfate anion, [S 3 O 10 ] 2– , that consists of three vertex connected [SO 4 ] tetrahedra. The distances S–O within the S–O–S bridges of the anion are remarkable asymmetric with distances of 155 and 169 pm, respectively. This structural feature is well reproduced by calculations on a PBE0/cc-pVTZ and a MP2/cc-pVTZ level of theory. Similar calculations allow also for an inspection of the yet unknown corresponding acid, H 2 S 3 O 10 . Also for this acid non-symmetric S–O–S bridges are predicted. The thermal behavior of Pb[S 3 O 10 ] is characterized by the loss of two equivalents of SO 3 at low temperature and the decomposition of intermediate Pb[SO 4 ] at higher temperature.

Description: The title ligand, [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazene, H L ( 1 ), was prepared. In a reaction with Hg(NO 3 ) 2 it forms the complex [Hg(C 26 H 22 Cl 2 N 6 O 2 )], [Hg L 2 ] ( 2 ). Both compounds were characterized by means of X-ray crystallography, CHN analysis, FT-IR, 1 H NMR, and 13 C NMR spectroscopy. In the structure of compound 1 , two independent fragments are present in the unit cell. They exhibit trans arrangement about the –N=N– double bond. The dihedral angles between two benzene rings in both fragments are 4.36 and 18.79 Å, respectively. Non-classic C–H ··· N hydrogen bonding and C–H ··· π interactions form a layer structure along the crystallographic ab plane [110]. In compound 2 , the Hg II atom is hexacoordinated by two tridentate [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazenide ligands through a N 2 O 2 set. In addition, in the structure of 2 , monomeric complexes are connected to each other by C–H ··· π stacking interactions, resulting in a 2D architecture. These C–H ··· π edge-to-face interactions are present with H ··· π distances of 3.156 and 3.027 Å. The results of studies of the stoichiometry and formation of complex 2 in methanol solution were found to support its solid state stoichiometry.

Description: RhCl 3 is shown to mediate unusual coupling reactions of tert -butyl acetylene. When RhCl 3 (H 2 O) n was heated with four equivalents of tert -butyl acetylene in methanol, the dinuclear complex [{Rh(μ-Cl)(CH 2 t Bu)( t BuC=CHCOCH 2 t Bu)} 2 ] ( 2 ) was isolated. A larger excess of tert -butyl acetylene (12 equiv.) resulted in the formation of the dimer [{η 5 -C 5 H 2 t Bu 2 (CH 2 t Bu)}Rh(μ-Cl) 3 Rh(C 24 H 42 O 2 )] ( 3 ). Both complexes were analyzed by single-crystal X-ray diffraction.

Description: Three pyrotechnic compositions based on ytterbium /polytetrafluoroethylene/Viton ® ( YTV ) 77/18/5, 82/13/5 and 87/8/5 wt.-% were compared to a baseline magnesium /polytetrafluoroethylene/Viton® ( MTV ) 60/35/5 wt.-% composition. YTV though energetically inferior to MTV both gravimetrically and volumetrically exhibit a radiance L λ (W · sr –1 · cm –2 ) superior to MTV in the important beta-band ( λ = 3.5–4.6 μm). This is assumed to be due to the selective emissivity of Yb 2 O 3 which is formed in the afterburning zone of YTV. The emissivity of Yb 2 O 3 is 7–10 times higher than that of MgO in the same spectral range. Due to the high density of ytterbium and the formulations based thereon YTV are promising candidates for autophagous nose cones for kinematic blackbody flares.

Description: Two novel coordination polymers based on mixed ligands, [Zn(dpb)(bdc)(H 2 O)] n ( 1 ) and [Cd(dpb)(bbdc)(H 2 O)(DMF)] n ( 2 ) [dpb = 1, 4-bis(pyridin-3-ylmethoxy)benzene, H 2 bdc = 1, 4-benzenedicarboxylate, H 2 bbdc = 4, 4′-dibenzenedicarboxylate], were synthesized under hydrothermal conditions. Compound 1 forms meso -helical chain and shows three fold interpenetrating architecture with 4-connected net {6 6} diamond topology. Compound 2 is a left- and right-handed helical layer, which are interacted by π–π stacking interactions to construct a 3D framework. The luminescent properties of the compounds are discussed.

Description: Energetic salts that contain nitrogen-rich cations and the 2-(dinitromethyl)-3-nitro-1, 3-diazacyclopent-1-ene anion were synthesized in high yield by direct neutralization reactions. The resulting salts were fully characterized by multinuclear NMR spectroscopy ( 1 H and 13 C), vibrational spectroscopy (IR), elemental analysis, density and differential scanning calorimetry (DSC), and elemental analysis. Additionally, the structures of the ammonium ( 1 ) and isopropylideneaminoguanidinium ( 9 ) 2-(dinitromethyl)-3-nitro-1, 3-diazacyclopent-l-ene salts were confirmed by single-crystal X-ray diffraction. Solid-state 15 N NMR spectroscopy was used as an effective technique to further determine the structure of some of the products. The densities of the energetic salts paired with organic cations fell between 1.50 and 1.79 g · cm –3 as measured by a gas pycnometer. Based on the measured densities and calculated heats of formation, detonation pressures and velocities were calculated using Explo 5.05 and found to to be 25.2–35.5 GPa and 7949–9004 m · s –1 , respectively, which make them competitive energetic materials.

Description: The stable dinuclear [Cu(μ-C 2 O 4 )Cu] 2+ entity is facially coordinated at each end by a N -nitrile functionalized triazamacrocycle, 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane ( L ), to generate a centrosymmetric compound [Cu 2 L 2 (μ-C 2 O 4 )](ClO 4 ) 2 · 4DMF ( 1 ) containing a bis-bidentate oxalate bridge. The variable-temperature magnetic measurement for the crystallographically characterized compound exhibits quite strong antiferromagnetic coupling interaction between two oxalate-linked Cu II atoms separated by 5.149 Å with a singlet-triplet energy gap of –345.5 cm –1 . On the other hand, a mononuclear Co III compound [Co L (N 3 ) 3 ] · 2.5H 2 O ( 2 ) with monodentate azide terminal groups was synthesized. Structural elucidation by X-ray diffraction shows that the compound has crystallographically imposed C 3 symmetry. Enantiomerically pure crystals were obtained upon crystallization indicated by a Flack parameter of 0.04(5).

Description: Single crystals as well as microcrystalline powders of K 3 NiO 2 were obtained via the azide/nitrate route, starting from stoichiometric mixtures of KN 3 , KNO 3 and NiO, at 923 K. According to temperature dependent X-ray investigations, K 3 NiO 2 exhibits a phase transition at approx. 423 K. Single crystal X-ray analysis at 500 K has shown that the high temperature modification ( β -K 3 NiO 2 , tP 12) crystallizes in P 4 2 / mnm ( Z = 2, a = 6.0310(9), c = 7.156(1) Å, R 1 = 0.037, R 2 = 0.105). The ambient temperature modification ( α -K 3 NiO 2 , tP 24) was refined as a racemic twin ( P 4 1 2 1 2/ P 4 3 2 1 2; a = 6.012(4), c = 13.843(8) Å, R 1 = 0.029, R 2 = 0.070 at 100 K; a = 6.0300(9), c = 14.065(3) Å, R 1 = 0.032, R 2 = 0.082 at 298 K) yielding nearly equal volumes for both enantiomorphs. The structural relationship within the A 3 MX 2 family is analyzed and displayed as a Bärnighausen tree. The essential feature of the low and high temperature phases are isolated NiO 2 3– dumbbells, which are linked by potassium atoms to infinite chains.

Description: A series of (azidomethyl)silanes [Me 3 SiCH 2 N 3 ( 1b ),Me 2 Si(CH 2 N 3 ) 2 ( 2b ), MeSi(CH 2 N 3 ) 3 ( 3b ), (CH 2 ) 4 Si(CH 2 N 3 ) 2 ( 4b ), and (CH 2 ) 5 Si(CH 2 N 3 ) 2 ( 5b )] was synthesized, starting from the corresponding (chloromethyl)silanes 1a–3a or (iodomethyl)silanes 4a and 5a . Compounds 1b–5b were characterized by NMR, IR, and Raman spectroscopy. The thermal stabilities of the (azidomethyl)silanes 1b–5b were investigated by DSC, and their impact and friction sensitivities were measured with standard BAM methods. According to these studies, the tris(azidomethyl)silane 3b has to be classified as an extremely sensitive compound.

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

Description: The first alkali metal carbodiimide cyanides Na 5 [CN 2 ] 2 [CN] and (Li,Na) 5 [CN 2 ] 2 [CN] were obtained from reaction of carbon with nitrogen gas pressure of 7 MPa in sodium melts without orwith admixture of Li 3 N, respectively. The crystal structures wererefined from single-crystal X-ray diffraction (Na 5 [CN 2 ] 2 [CN]: a = 7.201(2) Å, c = 6.605(4) Å, I 4/ mmm , R 1 = 0.028, wR 2 = 0.079; (Li 1.40 Na 3.60(3) ) 5 [CN 2 ] 2 [CN]: a = 7.0034(3) Å, Im m , R 1 = 0.038, wR 2 = 0.084). Whereas in Na 5 [CN 2 ] 2 [CN] a fully ordered arrangement of the anions is realized, in (Li,Na) 5 [CN 2 ] 2 [CN] both the alkali metal cations and the anions are disordered, with some site preference of lithium and sodium, leading to an increase of space group symmetry from I 4/ mmm for the pure sodium compound to Im m for the mixed Li/Na phase. Ammonothermal synthesis at 90 MPa leads to crystal growth of carbodiimide K 2 [CN 2 ] ( a = 5.762(1) Å , b = 5.669(1) Å ,c = 5.756(1) Å , β = 108.78(3)°, C 2/ m ) crystals in the cold zone of an autoclave. The crystal structure was analyzed and compared to the carbodiimide cyanides.