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A new layered compound, Hg5AsS2I3, has been synthesized in the quaternary system mercury/arsenic/chalcogen/halogen by a moderate-temperature solid-state reaction. The compound crystallizes in the space group C2/ c of the monoclinic system, and its structure consists of ∞1[Hg(1)2Hg(2)2As2/2S2] eight-membered-ring chains bridged by Hg atoms to form [Hg(1)2Hg(2)2Hg(3)As2/2S2] layers with inner- and interlayer electrostatic interactions between I and Hg. The optical properties were investigated by means of diffuse reflectance and FTIR spectra. The electronic band structures, along with density of states (DOS) calculations by DFT, indicate that the title compound is a semiconductor, and its optical absorption mainly leads to charge transitions from I-5p, As-4p and S-3p states to Hg-6s states, and both I(1) and I(2) atoms contribute to the top of the valence bands. [ABSTRACT FROM AUTHOR]

A new compound NaIn 3 S 5 has been obtained in the CaS–In 2 S 3 /NaBr system via a reactive flux method. NaIn 3 S 5 crystallizes in the orthorhombic space group Pbam (No. 55) with a = 12.4963(8) Å, b = 16.0811(10) Å, c = 3.8041(2) Å, and Z = 4. The NaIn 3 S 5 structure is characterized by a three dimensional framework consisting of interconnected tripartite-octahedral [ In 3 S 8 ] ∞ 1 infinite chains, with Na + cations residing in the one-dimensional channels along the c direction defined by S(1), S(2), S(3) and S(4) atoms. The optical reflectance measurement shows a band gap of 2.18 eV for NaIn 3 S 5 . Electronic structure calculation by the CASTEP code not only indicates that NaIn 3 S 5 is an indirect band gap semiconductor, but also explains why its experimental band gap is close to that of β-In 2 S 3 . [ABSTRACT FROM AUTHOR]

Abstract: In our investigation of rare earth sulfides in the AE-RE-Sn-S (AE=alkaline-earth, RE=rare earth) system, three isostructural quaternary sulfides have been obtained. These compounds adopt the Eu5Zr3S12 structure type and crystallize in the P-62m space group (no. 189); the crystal data are as follows: Sr2Y2.67Sn3S12, a =11.600(7)Å, c =3.948(3)Å, Z =1; Ca3La2Sn3S12, a =11.5997(6)Å, c =3.9407(4)Å, Z =1; Ca3Er2Sn3S12, a =11.448(3)Å, c =3.8780(11)Å, Z =1. Single-crystal analysis indicated that the crystal structures consist of three types of building block: RES7, AES6, and SnS6 units. The structure of Sr2Y2.67Sn3S12 is characterized by the trimer-chains along the c direction, which are connected into a 3-dimensional framework by the Sn atoms via S(1), S(2), and S(3), with Sr atoms filling in the channels along the c direction. The optical band gap of 1.45eV for Ca3La2Sn3S12 was deduced from the diffuse reflectance spectrum. [Copyright &y& Elsevier]

Abstract: In our investigation of non-centrosymmetric rare earth sulfides in the La3AgSnS7/KBr, LaAlGeS5/NaBr, HoAlGeS5/KBr, ErAlGeS5/NaBr, Er3AgGeS7/KBr and La3NaSnS7/NaBr systems, five compounds belonging to the R6B2C2Q14 family have been obtained. These compounds crystallize in the P63 space group, and the crystal data are as follows—La3AgSnS7: a =10.3780(15)Å, c =5.9900(12)Å, Z =2; La3Ge0.25GeS7: a =10.2970(15)Å, c =5.8120(12)Å, Z =2; Ho3Ge0.272(10)GeS7: a =9.6480(14)Å, c =5.7920(12)Å, Z =2; Er3Ge0.330(10)GeS7: a =9.5930(14)Å, c =5.8490(12)Å, Z =2; La3Sn0.25SnS7: a =10.2770(15)Å, c =6.0030(12)Å, Z =2. Single-crystal analysis indicated that the crystal structures consist of three types of building block: LnS n , MS4, and AgS3 (for La3AgSnS7) or MS6 units (for Ln3M x MS7, Ln=La, Ho, Er; M=Ge, Sn; 1/4≤ x ≤1/2), as any other compounds belonging to the R6B2C2Q14 family. Ln3M x MS7 (Ln=La, Ho, Er; M=Ge, Sn; 1/4≤ x ≤1/2) are deficient compounds with the B sites occupied partly by M(II), and/or M(IV). [Copyright &y& Elsevier]

Abstract: The alkaline-earth uranium chalcogenide Ba2Cu2US5 was obtained in a two-step reaction from BaS, Cu2S, and US2. Ba2Cu2US5 crystallizes in a new structure type in space group C2/m of the monoclinic system with two formula units in a cell of dimensions a=13.606(3)Å, b=4.0825(8)Å, c=9.3217(19)Å, and β=116.32(3)° (153K). The structure consists of layers separated by Ba atoms in bicapped trigonal-prismatic coordination. The two-dimensional layer is built from US6 octahedra and CuS4 tetrahedra. The connectivity of the MSn polyhedra within the layer in the [001] direction is oct tet tet oct tet tet. A μ eff value of 2.69(2) μ B/U was obtained from the magnetic susceptibility data. No magnetic transition was observed for Ba2Cu2US5 down to 2K. [Copyright &y& Elsevier]

Abstract: High-quality single crystals of RbInS2, CsInS2 were isolated from the halide flux as a major phase of the repeated fusion of CaS and In2S3 followed by slow cooling. RbInS2 and CsInS2 are practically isostructural with KInS2. RbInS2: C2/c, a =11.071(6)Å, b =11.068(1)Å, c =15.610(7)Å, β =100.36(3)°, V =1882(2)Å3, Z =16, d x =3.74g/cm3, R =6.38%, R w =6.42%. CsInS2: C2/c, a =11.197(3)Å, b =11.158(3)Å, c =16.358(4)Å, β =99.92(2)°, V =2013(2)Å3, Z =16, d x =4.12g/cm3, R =5.60%, R w =6.20%. The AInS2 (A=Rb, Cs) structure is characterized by double layers of vertex-sharing [In4S10] units that each consists of four [InS4] polyhedra. The charge-balancing alkali-metal cations are stuffed into the channels created by the packing of these anionic [In4S10] blocks. The optical reflectance measurements show a band gap of 3.3eV for RbInS2 and 3.4eV for CsInS2, suggesting that both are semiconductors. [Copyright &y& Elsevier]

Three new copper(II) complexes with isonicotinic acid N -oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H 2 O)] 2 (NO 3 ) 2 ···2H 2 O ( 1 ), [Cu(L)(phen)(H 2 O)] 2 (ClO 4 ) 2 ···2H 2 O ( 2 ), and [Cu(L)(phen)Br] 2 - [Cu(L)(phen)(H 2 O)] 2 Br 2 ···6H 2 O ( 3 ) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu 2 dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N -oxide anion is bidentate, being coordinated to two Cu(II) ions through its N -O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie-Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes. [ABSTRACT FROM AUTHOR]

Two new quaternary rare-earth chalcogenides, KHo2CuSe4 and KEr2CuSe4, were synthesized from the reactions of elements and binary selenides via a two-step flux technique. Single-crystal X-ray diffraction analyses indicate that both compounds crystallize in the orthorhombic KGd2CuS4 structure type with the space group Cmcm (No. 63) and Z=4. The indexed lattice constants and final R factors are as follows: KEr2CuSe4, a=4.061(1) A˚, b=13.748(4) A˚, c=14.150(3) A˚, V=790.1(3) A˚3, R=0.040, Rw=0.051; KHo2CuSe4, a=4.090(2) A˚, b=13.829(3) A˚, c=14.234(5) A˚, V=805.2(6) A˚3, R=0.046, Rw=0.052. The KLn2CuSe4 structure consists of three different building blocks: KSe6 trigonal prisms, LnSe6 octahedra and CuSe4 tetrahedra. The structure is characterized by edge-shared double octahedral Ln2Se10 units that are condensed into infinite chains along the a axis via trans-edge sharing. These double chains are further linked into a puckered layer in the a–b plane via edge-sharing and another corrugated layer in the a–c plane via corner-sharing with neighboring chains. Consequently, the structure actually forms a three-dimensional framework with additional feature from vertex-sharing CuSe4 tetrahedral chains. The K+ cations, located at the cavities defined by Se atoms, are filled in the channels along the a direction to provide appropriate Coulomb traps. Infrared spectra for both compounds show no absorption peaks between 4000 and 500 cm−1, which suggests an optical transparency in the long-wavelength infrared region. [Copyright &y& Elsevier]

Hg5AsS2I3 is prepared by solid-state reaction of a 3:1:1 molar mixture of Hg2I2, As, and S (pressed pellet, evacuated glass tube; 1. [ABSTRACT FROM AUTHOR]

The new title compounds are synthesized by solid state reactions of Ba, Ga2S9, Ge (Si), and S in a molar ratio of 2:4:1:4 (quartz tubes, 300 °C for 5 h, 650 °C for 10 h, and 980 °C for 5 d) and characterized by single crystal XRD, IR and UV/VIS/NIR diffuse reflectance spectroscopy, second harmonic generation measurements, laser-induced damage threshold measurements, and DFT electronic band structure calculations. [ABSTRACT FROM AUTHOR]

Abstract: Nonlinear optical (NLO) materials with strong second harmonic generation (SHG) responses are technologically and scientifically important for tunable lasers. This work puts forward a new strategy for designing promising infrared nonlinear optical (IR‐NLO) materials with strong SHG responses by strengthening both the static and induced contributions via the high orientation of NLO functional motifs. Two new polyselenides Rb2Ge4Se10 and Cs2Ge4Se10 are studied to verify the strategy, they have 2D infinite ∞ 2[Ge4Se10]2− layers comprising highly oriented distorted GeSe4 tetrahedra. Their large SHG signals (8.0 and 8.5 times that of commercial AgGaS2) can be ascribed to both the static contribution enhancement from the high orientation of the local dipole moment of GeSe4 tetrahedra and the induced contribution enhancement from terminal and SeSe bonded Se atoms. The results confirm the effectiveness of the proposed approaches, shedding light on the exploration of practical IR‐NLO materials with maximized performance. [ABSTRACT FROM AUTHOR]

Reactions of syn-2pyridinealdoxime (HL) with divalent metal salts in a mixed ethanol/acetonitrile solution resulted in two new metal complexes with different structures. The structure of the zinc complex, Zn4(L)4Cl2(μ3-OH)2 · 4CH3CN (1) features a 12-metallocrown-4 unit. The syn-2pyridinealdoxime ligand adopts a tridentate chelating and bridging coordination mode. The structure of Mn(HL)(SO4)(H2O) (2) contains a double chain along the b-axis, in which the Mn(II) cations are bridged by μ3-SO42− anions. The syn-2pyridinealdoxime ligand chelates with a Mn(II) ion using its two nitrogen atoms. These double chains are further interconnected into a 2D layer parallel to the ab-plane via hydrogen bonds between aqua ligands and the non-coordinated sulfate oxygen atoms. Results of magnetic measurements of complex 2 indicate that there is weak Curie–Weiss behavior with θ=−10(1) K indicating predominant antiferromagnetic interaction between the Mn(II) ions. Indication for magnetic low-dimensional magnetism could not be detected. [Copyright &y& Elsevier]

A new dinuclear oxomolybdate complex [(C6H4OCHN(CH2)3NHCOC6H4)2Mo2O3]·2H2O was obtained as black needle crystals by the reaction of MoCl3·3H2O with a specially designed tetradentate Schiff base ligand under solvothermal conditions. Single-crystal X-ray diffraction analysis indicates that it crystallizes in a monoclinic P21/c space group with a rare oxo-bridged dinuclear molybdenum structure. The structure is characterized by two MoO4N2 octahedra sharing a corner oxygen atom in a completely linear Mo&z.sbnd;O&z.sbnd;Mo arrangement. In addition to being the first example of nearly linear O&z.sbnd;Mo&z.sbnd;O&z.sbnd;Mo&z.sbnd;O arrangements, the present structure features a Mo&z.sbnd;O single bond at two ends, in sharp contrast with the known O&z.dbnd6;M&z.sbnd;O&z.sbnd;M&z.dbnd6;O (M=W, Re) units that contain M&z.dbnd6;O double bonds for terminal oxygen, due to the spatial chelating requirement of the long tetradentate Schiff base ligand. The completely linear Mo&z.sbnd;O&z.sbnd;Mo structure together with the relatively short Mo&z.sbnd;O distance of 1.8819(7) A˚ suggests the involvement of metal–oxygen π bonding. [Copyright &y& Elsevier]

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs2Cl][Ga3S6] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap. [ABSTRACT FROM AUTHOR]

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs2Cl][Ga3S6] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap. [ABSTRACT FROM AUTHOR]

Objective: To explore the diagnostic efficiency of DNA‐based and RNA‐based quantitative polymerase chain reaction (qPCR) analyses for periprosthetic joint infection (PJI). Methods: To determine the detection limit of DNA‐based and RNA‐based qPCR in vitro, Staphylococcus aureus and Escherichia coli strains were added to sterile synovial fluid obtained from a patient with knee osteoarthritis. Serial dilutions of samples were analyzed by DNA‐based and RNA‐based qPCR. Clinically, patients who were suspected of having PJI and eventually underwent revision arthroplasty in our hospital from July 2014 to December 2016 were screened. Preoperative puncture or intraoperative collection was performed on patients who met the inclusion and exclusion criteria to obtain synovial fluid. DNA‐based and RNA‐based PCR analyses and culture were performed on each synovial fluid sample. The patients’ demographic characteristics, medical history, and laboratory test results were recorded. The diagnostic efficiency of both PCR assays was compared with culture methods. Results: The in vitro analysis demonstrated that DNA‐based qPCR assay was highly sensitive, with the detection limit being 1200 colony forming units (CFU)/mL of S. aureus and 3200 CFU/mL of E. coli. Meanwhile, The RNA‐based qPCR assay could detect 2300 CFU/mL of S. aureus and 11 000 CFU/mL of E. coli. Clinically, the sensitivity, specificity, and accuracy were 65.7%, 100%, and 81.6%, respectively, for the culture method; 81.5%, 84.8%, and 83.1%, respectively, for DNA‐based qPCR; and 73.6%, 100%, and 85.9%, respectively, for RNA‐based qPCR. Conclusions: DNA‐based qPCR could detect suspected PJI with high sensitivity after antibiotic therapy. RNA‐based qPCR could reduce the false positive rates of DNA‐based assays. qPCR‐based methods could improve the efficiency of PJI diagnosis. [ABSTRACT FROM AUTHOR]

The first indiumsilicate oxysulfide Ba2In2Si3O10S ( 1) was obtained by an alkali polychalcogenide flux method through a high-temperature solid-state reaction. It crystallizes in the non-centrosymmetric space group Pca21 (No. 29), with a = 23.060(6), b = 5.2954(6), c = 8.779(2) Å, and Z = 4. Its three-dimensional (3D) framework is constructed from one-dimensional (1D) infinite ∞1[In2O7S2/2] double octahedral chains bridged by corner-sharing Si tetrahedral trimers [Si3O10]8-, yielding a 3D framework with the channels filled with Ba2+ cations along the b direction. It is unprecedented in that the two distorted indium octahedra in 1 face-share to form a [In2O7S2] dimer in indium oxides and oxide chalcogenides. [ABSTRACT FROM AUTHOR]

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy. [ABSTRACT FROM AUTHOR]

Three new diamond-like compounds with the formula of I2−II−IV−VI4 (I=Cu; II=Mg; IV=Si, Ge; VI=S, Se) have been synthesized via traditional high-temperature solid-state reactions and structurally characterized by single crystal X-ray diffraction analysis. All the three compounds crystallize in the space group Pmn21 in the wurtzite-type superstructure with a=7.563(4), b=6.448(3), c=6.179(3)Å, Z=2 for Cu2MgSiS4 (1); a=7.953(5), b=6.797(4), c=6.507(4)Å, Z=2 for Cu2MgGeS4 (2); a=7.638(4), b=6.515(4), c=6.225(3)Å, Z=2 for Cu2MgSiSe4 (3). All atoms in these compounds are tetrahedrally coordinated. Optical diffuse reflectance UV/Vis/NIR spectra indicate that compounds 1 and 2 have the band gaps of 3.20 and 2.36eV, respectively. Electronic structure calculations using the CASTEP code indicate that they are all direct band gap compounds. [ABSTRACT FROM AUTHOR]

Hydrothermal reactions of N,N-bis(phosphonomethyl)aminoacetic acid (HO2CCH2N(CH2PO3H2)2) with metal(II) salts afforded two new metal carboxylate-phosphonates, namely, Pb2[O2CCH2N(CH2PO3)(CH2PO3H)]·H2O (1) and {NH3CH2CH2NH3}{Ni[O2CCH2N(CH2PO3H)2](H2O)2}2 (2). Among two unique lead(II) ions in the asymmetric unit of complex 1, one is five coordinated by five phosphonate oxygen atoms from 5 ligands, whereas the other one is five-coordinated by a tridentate chelating ligand (1 N and 2 phosphonate O atoms) and two phosphonate oxygen atoms from two other ligands. The carboxylate group of the ligand remains non-coordinated. The bridging of above two types of lead(II) ions through phosphonate groups resulted in a 〈002〉 double layer with the carboxylate group of the ligand as a pendant group. These double layers are further interlinked via hydrogen bonds between the carboxylate groups into a 3D network. The nickel(II) ion in complex 2 is octahedrally coordinated by a tetradentate chelating ligand (two phosphonate oxygen atoms, one nitrogen and one carboxylate oxygen atoms) and two aqua ligands. These {Ni[O2CCH2N(CH2PO3H)2][H2O]2}− anions are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a 〈800〉 hydrogen bonded 2D layer. The 2H-protonated ethylenediamine cations are intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Results of magnetic measurements for complex 2 indicate that there is weak Curie–Weiss behavior with θ=−4.4 K indicating predominant antiferromagnetic interaction between the Ni(II) ions. Indication for magnetic low-dimension magnetism could not be detected. [Copyright &y& Elsevier]

Three new divalent transitional metal succinates with an additional bipy (bipy=4,4′-bipyridine) ligand have been synthesized by hydrothermal reactions and structurally determined. The structure of [Cu(C4H4O4)(bipy)(H2O)2] · 2H2O (1) features a 3D open framework formed by 1D [Cu(bipy)]2+ chains along the diagonal axis of b and -c that are interconnected by Cu(C4H4O4) helixes along the c-axis. The lattice water molecules are located at the cavities of the framework. In Zn(C4H4O4)(bipy) (2), each zinc cation is octahedrally coordinated by two chelate carboxylate groups from two succinates and 2 N atoms from two bipy molecules, and the ZnO4N2 octahedra are interconnected by bridging succinate ligands into a 1D chain along the 〈0 1 1〉 direction. Such chains are further linked into a 〈0 1 1〉 layer via π–π stacking interaction between the pyridine rings. In [Co(bipy)(H2O)4] (C4H4O4) · 4H2O (3), each pair of octahedral cobalt(II) ions is bridged by a bipy ligand, resulting in a 1D [Co(bipy)(H2O)4]2+ chain, and the succinate ligands and lattice water molecules are sandwiched between two [Co(bipy)(H2O)4]2+ chains to form a 〈0 1 1〉 layer via hydrogen bonding. The layers are further interconnected into a 3D network via hydrogen bonds among carboxylate oxygen atoms, aqua ligands, and lattice water molecules. [Copyright &y& Elsevier]

A novel chiral open-framework structural hexanary chalcogenoborate, (K3I)[SmB12(GaS4)3] (1), was obtained by a facile approach using boron as the reducing reagent; it shows weak SHG-activity and is transparent in the mid-IR region. [ABSTRACT FROM AUTHOR]

Titelbild: Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance (Angew. In ihrem Forschungsartikel auf S. 4700 beschreiben S. Zhu et al. die De-novo-Synthese von hydroxyliertem Benzofuran und die Realisierung einer kollektiven Totalsynthese von hydroxylierten benzofuranhaltigen Naturstoffen. In der Zuschrift auf S. 4860 beschreiben J. H. van Esch et al. die Herstellung biomimetischer, unter Spannung erstarrender Hydrogele durch die Selbstassemblierung molekularer Gelbildner. [Extracted from the article]

Single crystals of the new title compound are obtained from an alkali polychalcogenide flux consisting of K2S, S, In, SiO2, and BaCl2 in a molar ratio of 2:2:4:1:4 (evacuated quartz tubes, 1. [ABSTRACT FROM AUTHOR]

Single crystals of Na2In2MS6 (M: Si, Ge) are prepared by solid state reaction of a 3:1:1:5 molar mixture of Na2S, In, Si (Ge), and S (evacuated quartz tubes, 1. [ABSTRACT FROM AUTHOR]

Single crystals of BaGeOSe2 are prepared by solid state reaction of a stoichiometric mixture of GeO2, Ba, Se, and extra KI as a flux (evacuated quartz tubes, 1. [ABSTRACT FROM AUTHOR]

Cu2MgSiS4 (I), Cu2MgGeS4 (II), and Cu2MgSiSe4 (III) are synthesized by solid state reactions of stoichiometric mixtures of the elements (quartz tube, 950 °C, 5 d). [ABSTRACT FROM AUTHOR]