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The incorporation of [Mn(2,2‘-bipy)2]2+ with thioarsenate resulted in the formation of two novel compounds, [Mn3(2,2‘-bipy)3(AsVS4)2]n·nH2O (1) and Mn2(2,2‘-bipy)As2IIIS5 (2), in which the main-group chalcogenide framework is incorporated with a [tm(2,2‘-bipy)m]n+ complex. Meanwhile, the tetrathioarsenate(V) anion acts as a new μ3-1κS:1,2κS‘:2,3κS‘ ‘:3κS‘ ‘‘ ligand in 1, in which all four S atoms of the [AsVS4]3- anion are coordinating to metal. As a result, the two compounds exhibit semiconducting properties (Eg = 2.18 eV (1) and 1.83 eV (2)) and strong blue photoluminescence, with the emission maximum occurring at about 440 nm. Magnetic measurements show that both compounds have AF ordered states with Neel temperatures of 19 and 24 K for 1 and 2, respectively.

Four cyano-bridged 4f−3d (lanthanide−transition metal) bimetallic assemblies, [Sm(DMF)2(H2O)3(μ-CN)3M(CN)3]n·nH2O (M = Fe (1), Co (2)) with 2-D monolayered structures and [Sm(DMF)(H2O)3(μ-CN)4M(CN)2]n·nH2O (M = Fe (3), Co (4)) with 2-D bilayered structures (DMF = N,N-dimethylformamide), were rationally prepared by a facile approach, a ball-milling method, and characterized by X-ray diffraction studies and magnetic measurements. The unprecedented 2-D bilayered 4f−3d hexacyanometalates (3 and 4) were obtained by controllably reducing the half amount of DMF in the reactive system in comparison with 1 and 2 through a ball-milling method.

A new viologen(4,4′-bipyridinium)-based compound [(CH3)2–4, 4′-H2bipy][FeCl4]2 (1) (bipy = bipyridine), in which the (CH3)2–4,4′-H2bipy (MQ 2+ ) was generated in situ, has been synthesized via a solvothermal reaction and structurally characterized by single crystal X-ray diffraction. The crystal structure analysis revealed that compound 1 is characteristic of an isolated structure, based on MQ 2+ moieties and Fe3+ ions terminally coordinated by four chlorine ions. The MQ 2+ moieties and (FeCl4)− anions connect together via hydrogen bonds to yield a 3-D supramolecular framework. Fluorescent study shows that compound 1 displays strong and broad emission bands.

The metalloporphyrin [(ZnTPP)2( μ2-4,4'-bipy)], (H2TPP = 5,10,15,20-tetraphenyl-21H,23H-porphyrin; 4,4'-bipy = 4,4'-bipyridine), has been synthesised via a solvothermal reaction and structurally characterised by single-crystal X-ray diffraction. It features a planar porphyrin macrocycle and an embedded ZnII ion coordinating to four pyrrole nitrogen atoms and one 4,4'-bipy nitrogen atom. A photoluminescent and theoretical study shows that the complex exhibits an emission in the red region, attributed to ligand to ligand charge-transfer.

Two series of novel complexes, [Ln(dca)2(Phen)2(H2O)3](dca)·(phen) (Ln = Pr (1), Gd (2), and Sm (3), dca = N(CN)-, phen = 1,10-phenanthroline) and [Ln(dca)3(2,2‘-bipy)2(H2O)]n, (Ln = Gd (4), Sm (5), and La (6), 2,2‘-bipy = 2,2‘-bipydine), have been synthesized and structurally characterized by X-ray crystallography. The crystal structures of the first series (1−3) are isomorphous and consist of discrete [Ln(dca)2(Phen)2(H2O)3]+ cations, dca anions, and lattice phen molecules; whereas the structures of the second series (4−6) are characterized by infinite chains [Ln(dca)3(2,2‘-bipy)2(H2O)]n. The Ln(III) atoms in all complexes are nine-coordinated and form a distorted tricapped trigonal prism environment. The three-dimensional frameworks of 1−6 are constructed by intermolecular hydrogen bond interactions. Variable-temperature magnetic susceptibility measurements for complexes 1, 2, 4, and 5 indicate a Curie−Weiss paramagnetic behavior over 5−300 K.

Four new quaternary Ag-containing group 5 chalcogenides, KAg2NbSe4 (1), KAg2TaSe4 (2), K3Ag3Nb2S8 (3), and K3Ag3Ta2S8 (4), have been prepared through the use of molten alkali metal polychalcogenide...

A novel zinc porphyrin, Zn[(tcpp)(thf)2] (1) (tcpp = meso-tetra(4-carboxyphenyl)porphyrin; thf = tetrahydrofuran), has been prepared via a solvothermal reaction and structurally characterized by single crystal X-ray diffraction. The zinc ion coordinates to four nitrogen and two oxygen atoms. The substance crystallizes orthorhombically in the space group Cmca with a = 30.8367(6), b = 8.7099(5), c = 15.3526(2) Å, V = 4123.5(3) Å3, C56H44N4O10Zn, Z = 4, Mr = 998.34, Dc = 1.608 g/cm3, S = 0.991, μ(MoKα ) = 0.673 mm–1, F(000) = 2072, R = 0.0555 and wR = 0.1338. Photoluminescent investigation shows that complex 1 exhibits an emission in the blue region. The spectral data of FT–IR were also reported.

The compound [Me4bim][CdCl4] (Me4bim = 1,1′,3,3′-tetramethyl-2,2′-bi-1 H-imidazolium), has been prepared via a solvothermal reaction and has an isolated (0-D) structure. It displays an emission in the blue region that is ascribed to ligand-to-ligand charge transfer on the basis of a theoretical investigation.

A novel quaternary metal chalcogenide Hg3ZnSe3Br2 (1) was prepared via a solid-state reaction method and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the space group P-3 of the hexagonal system with two formula units in a cell: a = 7.383(7) A, c = 10.924(9) A, V = 515.6(8) A3, FW = 1063.84, Dc = 6.852 g/cm3, S = 0.713, μ(MoKα) = 65.083 mm−1, F(000) = 884, R = 0.1377 and wR = 0.2720. Compound 1 is characterized by a 2-D layered motif, which is constructed from the interconnected 12-membered Hg6Br6 rings with a chair-like conformation.

A novel iron porphyrin [FeTCPP] n [TCPP = meso-tetra(4-carboxyphenyl)porphyrin] has been synthesised via a hydrothermal reaction and structurally characterised. It has a two-dimensional structure and is thermally stable up to 320°C. UV–Vis, FT–IR and fluorescence data are also reported. Porphyrins have interesting roles in nature such as in green leaves and red blood cells, as well as applications in medicine, catalysis, optics, conductive materials, magnetism and solar energy conversion.

The first crystalline TPPS complex [Zn(en)TPPS][Zn(en)3] (where en is ethylenediamine and TPPS is tetraphenylporphyrin tetrasulfonic acid) has been synthesised via a solvothermal reaction and structurally characterised by a single-crystal X-ray diffraction. Zn(en)TPPS][Zn(en)3has discrete [Zn(en)TPPS]2–and [Zn(en)3]2+moieties, which are interconnected via hydrogen bonds to form a three-dimensional supramolecular framework that possesses a large void space (1507.6 Å3) corresponding to 22.5% of the unit-cell volume. The UV-Vis spectrum and photoluminescence have also been studied in detail.

A novel N,N'-diethyl-4,4'-bipyridine copper complex, [Cu2Cl4][(C2H5)2-4,4'-bipyridine] (1), has been obtained in situ through a solvothermal reaction and structurally characterised by X-ray diffraction. Complex 1 comprises discrete Cu2Cl4 moieties and (C2H5)2-4,4'-bipyridine molecules interlinked via hydrogen bonding interactions to give a three-dimensional supramolecular open framework. Photoluminescent study shows that the complex exhibits an emission in the green region. Theoretical study reveals that the emission is attributed to the π → π* charge-transfer interaction of the (C2H5)2-4,4'-bipyridine moieties.

A new pyridine-2-carboxylic acid complex, [Cu(2-PyCOOH)2(H2O)2]Cl2, has been prepared in situ through a hydrothermal reaction and its structure comprises discrete [Cu(2-PyCOOH)2(H2O)2]2+ cations and chloride anions which are interlinked via hydrogen bonding interactions to give a 3-D supramolecular motif. Photoluminescent study shows that the complex exhibits an emission in the blue region. Theoretical studies reveal that the emission can be ascribed to metal-to-ligand charge transfer.

Hydrothermal reaction of FeCl3 and nicotinic acid gave a novel, trinuclear metal-nicotinato complex Fe3(O)(C6NO2H5)6(H2O)3·3H2O·7Cl. An X-ray crystal structure analysis reveals that it features an isolated structure. The crystal belongs to the rhombohedral, space group R--3c with a = b = 19.9410(6) Å, c = 30.505(1) Å, V = 10504.9(6) Å3, Z = 6, C36H42Cl7Fe3N6O19, Mr = 1278.46, Dc = 1.213 g cm−3, S = 0.980, μ(Mo Kα) = 0.936 mm−1, F(000) = 3894, R = 0.0694 and wR2 = 0.1579. The iron atom has a slightly distorted octahedral geometry, coordinated by six oxygen atoms. All three octahedrons interconnect to each other via corner-sharing an oxygen atom, yielding an oxo-centred, trinuclear iron cluster. The [Fe3(O)(C6NO2H5)6(H2O)3]7+ species, lattice water molecules and chloride ions are held together via hydrogen bonds to construct a three-dimensional (3-D) open framework, with a large void space (2803.9 Å3) corresponding to 26.7% of the unit-cell volume (10504.9 Å3).

The compound [Hg3S2CI2] has been obtained by solid-state reactions. It crystallises in the acentric space group R3of the rhombohedral system with six formula units in a cell [ a = b = 12.654(3), c = 7.753(4) Å, V = 1075.1(6) Å3, CI2Hg3S2, Mr= 736.79, Dc= 6.828 g cm−3, S = 0.987, μ(Mo Kα) = 65.308 mm−1, F(000) = 1836, R = 0.0631 and wR = 0.1443] and is characterised by a 3-D framework structure, which is composed of interconnected right-handed helices formed by tetrahedral Hg atoms. Optical absorption spectra reveal the presence of an optical bandgap of 2.51 eV and the composition Hg3S2CI2is confirmed by semiquantitative microscope analysis.

A novel viologen(4,4′-bipyridinium)-based complex ZnCl 3 (4-methyl-4,4′-bipyridinium) ( 1 ), in which the 4-methyl-4,4′-bipyridinium (MQ + ) was generated in situ, has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. The title complex features an isolated structure, based on the MQ + ligand coordinating to a zinc atom that is further terminally bound by three chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region, which may originate from π → π ∗ charge-transfer interaction of the MQ + ligand.

The title inorganic-organic hybrid complex, [CdBr2(C(10)H(8)N(2))]n, features two-dimensional [CdBr2(4,4'-bipy)]n (4,4'-bipy is 4,4'-bipyridine) neutral networks, based on the octahedral Cd atom coordinated by four mu2-Br and two mu2-4,4'-bipy at trans positions, yielding a CdBr(4)N(2) octahedron. It crystallizes in the orthorhombic system (Cmmm). All the crystallographically independent atoms are on special positions, namely Cd on mmm, Br on mm, N on mm2, and C on sites of symmetry m or mm2. Optical absorption spectroscopy reveals the presence of an optical gap of 3.76 eV, indicating that the complex is a wide-gap semiconductor. Photoluminescence investigation reveals that the complex displays strong colour-tunable emissions, which might originate from a ligand-to-ligand charge-transfer (LLCT) transition. Thermogravimetric differential thermal analysis shows that the complex is thermally stable up to 493 K.

(4,4′-H2bipy)[HgBr4] · H2O (1), has been synthesized via hydrothermal reaction. The title compound features an isolated structure, based on discrete 4,4′-H2bipy moieties, lattice water molecules and tetrahedral mercury atoms terminally coordinated by four bromine atoms. The 4,4′-H2bipy moieties, lattice water molecules and tetrabromo-mercury dianions are linked via hydrogen bonds. Optical absorption spectrum reveals that the presence of an optical gap of 2.53 eV, indicating that compound 1 exhibits a semiconductor property. Photoluminescent investigation reveals that the title compound displays a strong blue-light emission, which maybe originates from π → π∗ charge-transfer interaction of 4,4′-H2bipy. IR, SEM/EDS and thermogravimetry-differential thermal analyses (TG-DTA) are also presented.

The title compound, [Zn2(HO3PCH2CH2COO)2(C10H8N2)2(H2O)2], was synthesized by the hydro­thermal method. Two zinc ions are linked by two 2-carboxy­ethyl­phospho­nic acid ligands to form a dimer. These dimers are located on inversion centres and are further inter­linked by hydrogen bonds and π–π stacking inter­actions to form a three-dimensional supramol­ecular structure.

The reactions of silver(I) cyanide with tetraalkylammonium salts in anhydrous tetrahydrofuran (THF) under solvothermal conditions and then diffused with ether lead to two novel mixed halogeno(cyano)argentates(I) with efficient luminescence.

The self-assembly of LiBr and bis(diphenylphosphineoxo)ethane (dppe-O) in tetrahydrofuran (THF) and further diffusion with n-pentane gave rise to a new coordination polymer formulated as [Li 2 (dppe-O) 3 Br 2 ] n and has been shown by X-ray diffraction analysis to be a 2-D noninterpenetrating honeycomb-like layer of (6,3) topology containing 42-membered rings with 1-D hydrophobic channels. These 2-D layers stack together tightly through weak hydrogen bonding and strong π...π stacking interactions to form a 3-D nanoporous structure.

Zn(C5H4NCO2H)2(H2O)2 • 2Cl (1) has been synthesized in situ via hydrothermal reaction and characterized by single crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 6.342(2), b = 10.164(3), c = 13.717(4) Å, β = 113.62(1)°, C12H14Cl2N2O6Zn, Mr = 418.54, V = 810.1(4) Å3, Z = 2, Dc = 1.716 g/cm3, S = 1.063, µ(MoKα) = 1.875 mm-1, F(000) = 424, R = 0.0276 and wR = 0.0780. The crystal structure analysis of 1 reveals that the title compound features a structure consisting of isolated units, based on discrete chloride ions and octahedral zinc cations six-coordinated by four oxygen and two nitrogen atoms. The chloride ions and [Zn(C5H4NCO2H)2(H2O)2]2+ moieties are interconnected by hydrogen bonding interactions to yield a 3-D supramolecular framework. Luminescent investigation reveals an emission in blue region, which may be originating from π→π* charge-transfer interaction of the pyridine-2-carboxylic acid.

A novel terbium-containing fluorescent material, [Tb(CH3COO)2(H2O)3]Cl (1), has been prepared by a facile approach, i.e. an ultrasonic synthesis. Compound 1 has been structurally characterized via single-crystal X-ray diffraction and it crystallizes in the space group P21/n of the monoclinic system with four formula units in a cell. Compound 1 features a novel one-dimensional (1-D) chain-like structure. The 1-D chains are interconnected by hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that compound 1 displays strong emission bands identified as the characteristic emissions of 5D4 → 7FJ (J = 3, 4, 5, 6) of Tb3+.

A novel zinc-isonicotinic acid complex [Zn(Hini)(Ini)Cl]n (1) (Hini = isonicotinic acid; Ini = deprotoned isonicotinic acid) has been synthesized via a hydrothermal reaction and structurally characterized by a single-crystal X-ray diffraction. Complex 1 crystallizes in the space group P21/c of the monoclinic system with four formula units in a cell: a = 7.654(4), b = 13.540(7), c = 14.213(3) Å, β = 122.21(1), V = 1246.2(10) Å3, C12H9ClN2O4Zn, Mr = 346.05, Dc = 1.844 g/cm3, S = 1.017, µ(MoKα) = 2.199 mm-1, F(000) = 696, R = 0.0206 and wR = 0.0500. Complex 1 is characteristic of a novel one-dimensional (1-D) chain-like structure. Photoluminescence investigation reveals a strong emission, which may originate from π → π* charge-transfer interaction of the isonicotinic acid ligand.

The 4f-3d heterometallic complexes [Nd(L)3(H2O)2]2(ZnCl4)3n • 4nH2O (1) (L = isonicotinic acid) and [Sm(L')3(H2O)2]2(ZnCl4)n • 2nH2O (2) (L' = nicotinic acid) have been obtained by hydrothermal reactions and structurally characterized by X-ray single-crystal diffractions. Both complexes feature an infinite 1-D polycationic chain-like structure. Photoluminescent investigations reveal that both complexes display totally different emissions. The emission of complex 1 is attributed to the π → π* charge-transfer interaction of the isonicotinic acid. Complex 2 exhibits emissions in a wide range, and the emissions are ascribed to the characteristic emissions of 4G5/2 → 6HJ (J = 5/2, 7/2, 9/2, 11/2) of Sm3+ ions.

Four complexes, Ln2(C6H5SO2)6(H2O)3 · 2.25H2O (C6H5SO2 = 2-thiopheneacetic acid, Ln = Ce (1), Pr (2), Nd (3), Sm (4)), have been synthesized with hydrothermal route. The X-ray diffraction analyses reveal that they are characterized by the 1D structure and fluorescence studies show they display interesting luminescent properties in solid state.

To explore the correlation between cytokine levels and the pathological changes under arthroscopy in knee osteoarthritis of Blood Stasis type.From 2009.2 to 2010.3, 90 patients with knee osteoarthritis were reviewed. Among the patients, 17 patients were male and 73 patients were female, ranging in age from 40 to 70 years, averaged 57.2 years, the duration of the disease ranged from 1 month to 10 years, with a mean of 3.4 years. Thirty-one patients had osteoarthritis in left knee, and 59 patients in right knee. The patients had the syndrome of blood stasis. All the patients had pain and morning stiffness; most patients had joint interlocking; and all the patients didn't have joint swelling. The synovial fluid was collected before surgery, and ELISA was used to detect the contents of interleukin-1beta and transforming growth factor-beta1. At the same time, the pathological changes of the joint were observed under the arthroscopy. Based on the above datum analysis, the severity of knee osteoarthritis of blood stasis type was studied, and the correlation between different types of pathological changes under arthroscopy and cytokine levels was analyzed.The contents of IL-1beta and TGF-beta1 in synovial fluid were (28.18 +/- 5.57) pg/ml and (51.69 +/- 6.56) pg/ml respectively. The level of IL-1beta of grade III-IV cartilage degeneration was (30.65 +/- 3.48) pg/ml, which was significantly higher than (20.55 +/- 3.50) pg/ml of grade I-II cartilage degeneration group; the level of TGF-beta1 of grade I-II cartilage degeneration was (58.18 +/- 3.98) pg/ml,which was significantly higher than (49.59 +/- 5.83) pg/ml of grade II-IV cartilage degeneration group. IL-1beta and cartilage degeneration was positively correlated, the correlation coefficient was 0.744; TGF-beta1 and cartilage degeneration was negatively correlated, the correlation coefficient was -0.563. The level of IL-1beta of grade II-III synovial hyperplasia was (33.48 +/- 2.95) pg/ml, which was significantly higher than (25.40 +/- 4.50) pg/ml of grade I synovial hyperplasia group; IL-beta was positively correlated with synovial hyperplasia, the cor- relation coefficient was 0.801. The levels of IL-1beta of grade I osteophyte formation was (34.18 +/- 2.69) pg/ml, which was significantly higher than (25.74 +/- 4.48) pg/ml of grade 0 osteophyte formation group; the level of TGF-beta 1 of grade 0 osteophyte formation was (53.11 +/- 6.78) pg/ml, which was higher than (48.21 +/- 4.47) pg/ml of grade I osteophyte formation group. IL-1beta was positively correlated with osteophyte formation, the correlation coefficient was 0.762; TGF-beta1 was negatively correlated with osteophyte formation, the correlation coefficient was - 0.340.All the patients with knee osteoarthritis identified as blood stasis syndrome have pathological changes such as articular cartilage degeneration and synovial hyperplasia. The level of IL-1beta has important reference value to estimate the severity of cartilage degeneration, synovial hyperplasia and osteophyte proliferation.

Two novel metal sulfur chlorides – Zn 6 S 5 Cl 2 ( 1 ) and Hg 3 ZnS 2 Cl 4 ( 2 ) – were obtained by solid-state reactions and structurally characterized by single-crystal X-ray diffraction. Compound 1 is characteristic of a 1-D tunnel-like structure, which connects to each other to construct a 3-D framework with the chlorine atoms locating at the voids. Compound 2 crystallizes in the acentric space group P 6 3 mc of the hexagonal system. Compound 2 features a 2-D layered motif, which is composed by the interconnected 12-membered Hg 6 S 3 Cl 3 rings with chair-like conformation. There are ZnSCl 3 tetrahedra located between the layers, yielding a sandwich-like structure. TG-DTA measurement shows that compound 1 is thermally stable up to 220 °C. Optical absorption spectra reveal the presence of sharp optical gap of 2.71 and 2.65 eV for 1 and 2 , respectively.

Fourteen cyano-bridged two-dimensional bimetallic 4f—3d complexes are synthesized and their structures are characterized by XRD.

Hydrothermal reaction of NdCl 3 ·6H 2 O, HgCl 2 and isonicotinic acid gave a bimetallic 4f-5d metal-isonicotinato complex [Nd(C 6 NO 2 H 5 ) 3 (H 2 O) 2 ] 2n · (3nHgCl 4 ) · (4nH 2 O) (1) and an X-ray crystal structure analysis reveals that it features a one-dimensional polycationic chain-like structure. The crystal belongs to the monoclinic, space group C2/c with a = 24.208(1), b = 20.842(1), c= 15.379(1) A, β=127.759(1)°, V=6134.5(7) A 3 , Z = 4, C 36 H 46 Cl 12 Hg 3 N 6 Nd 2 O 20 , M r = 2198.44, D c = 2.380 g/cm 3 , S = 0.986, μ(MoK α )=9.738 mm -1 , F(000)=4112, R = 0.0384 and wR = 0.0848. The neodymium atom has a distorted square anti-prism geometry, coordinated by eight oxygen atoms. Each mercury atom is bound by four chlorine atoms to form a HgCl 4 2- tetrahedron. The [Nd(C 6 NO 2 H 5 ) 3 (H 2 O) 2 ] 2n 6n+ species, HgCl 4 2 anions and lattice water molecules are held together via hydrogen bonds to form a three-dimensional framework.

The title compound, C(4)H(4)N(6)S(2), was synthesized by the reaction of 3-mercapto-1H-1,2,4-triazole with sodium hydrox-ide in ethanol. The mol-ecule possesses a crystallographically imposed twofold axis. Inter-molecular N-H⋯N hydrogen bonds link the mol-ecules into chains along the c axis.

Two structural series, including seven isomorphous heterodinuclear complexes, [Ln(DMSO)4(H2O)3(mu-CN)M(CN)5].H2O ([La-Fe] (1), [Pr-Fe] (2), [Pr-Co] (3), [Nd-Fe] (4), [Nd-Co] (5), [Sm-Fe] (6) and [Sm-Co] (7)), and seven isostructural 2-D stair-like cyano-bridged bimetallic assemblies, [Ln(DMSO)2(H2O)(mu-CN)4M(CN)2]n ([La-Fe]n (8), [Pr-Fe]n (9), [Pr-Co]n (10), [Nd-Fe]n (11), [Nd-Co]n (12), [Sm-Fe]n (13) and [Sm-Co]n (14)) (DMSO = dimethylsulfoxide), have been rationally prepared by a facile approach, a ball-milling method, and characterized by X-ray diffraction and magnetic measurements. The isomorphous structures, in conjunction with the diamagnetism of the Co(3+) and La(3+) ions, allow an approximation to the nature of coupling between the iron(III) and lanthanide(III) ions in the Ln(3+)-Fe(3+) complexes. The Ln(3+)-Fe(3+) interaction is ferromagnetic for the dinuclear [Pr-Fe] (2), [Nd-Fe] (4), and [Sm-Fe] (6) systems and for the 2-D [Pr-Fe]n (9), [Nd-Fe]n (11), and [Sm-Fe]n (13) assemblies.

Two isostructural metal chalcogenides, Hg{sub 2}Te{sub 2}Br{sub 2} (1) and Hg{sub 2}Te{sub 2}I{sub 2} (2), were obtained by solid-state reactions and structurally characterized. Compounds 1 and 2 crystallize in the acentric space group P4{sub 3}2{sub 1}2 of the tetragonal system with eight formula units in a cell: a=10.2388(9), c=14.480(2) A, V=1518.0(3) A{sup 3}, R {sub 1}/wR {sub 2}=0.0670/0.1328 for 1 and a=10.711(3), c=15.025(8) A, V=1724(1) A{sup 3}, R {sub 1}/wR {sub 2}=0.0637/0.1233 for 2. Both compounds are characterized by a three-dimensional (3-D) framework structure, which is composed by interconnected left-handed helices formed by both tetrahedral and trigonal Hg atoms. Optical absorption spectra of 1 and 2 reveal the presence of sharp optical gaps of 2.06 and 1.85 eV, respectively, suggesting that both materials are semiconductors. TG-DTA measurements show that both compounds are thermally stable up to 200 deg. C. The composition of both compounds is well confirmed by the semiquantitative microscope analyses. - Graphical abstract: A new family of IIB {sub 2} Q {sub 2} X {sub 2} system, possessing an acentric nature that allows them to be a potential NLO material, has been synthesized via solid-state reactions. The crystal structures are characterized by a 3-D framework structure, comprising ofmore » interconnected left-handed helices. Optical absorption spectra show that both compounds are excellent candidate for potential photoelectric materials.« less

A new quaternary cadmium and mercury pnictidehalide semiconductor (Hg2Cd2As2Br)Br (1) has been prepared by the solid-state reaction of HgBr2 with elemental Cd and As at 420 degrees C. Compound 1 crystallizes in the space group Pmma of the orthorhombic system with two formula units in a cell: a = 8.791(4) A, b = 4.701(2) A, c = 9.779(6) A, V = 404.2(3) A(3). The structure of 1 is composed of parallel slabs bridged by linearly coordinated Hg atoms to form a 3D cationic network with the channels occupied by discrete Br anions, in which the layer consists of interlinks of linear (HgAs2Br2) tetrahedral chains and (CdAs2Br) trigonal chains. The optical properties were investigated in terms of the diffuse reflectance and Fourier transform infrared spectra. The electronic band structure along with the density of states (DOS) calculated by the DFT method indicate that compound 1 is a semiconductor with an indirect band gap and that the optical absorption mainly originates from the charge transitions from the Br2-4p and As-4p to Cd-5s and Hg-6s states.

The incorporation of [Mn(2,2'-bipy)2]2+ with thioarsenate resulted in the formation of two novel compounds, [Mn3(2,2'-bipy)3(As(V)S4)2]n.nH2O (1) and Mn2(2,2'-bipy)As2(III)S5 (2), in which the main-group chalcogenide framework is incorporated with a [tm(2,2'-bipy)m]n+ complex. Meanwhile, the tetrathioarsenate(V) anion acts as a new mu3-1kappaS:1,2kappaS':2,3kappaS":3kappaS'" ligand in 1, in which all four S atoms of the [As(V)S4]3- anion are coordinating to metal. As a result, the two compounds exhibit semiconducting properties (Eg = 2.18 eV (1) and 1.83 eV (2)) and strong blue photoluminescence, with the emission maximum occurring at about 440 nm. Magnetic measurements show that both compounds have AF ordered states with Néel temperatures of 19 and 24 K for 1 and 2, respectively.

Two series of novel complexes, [Ln(dca)(2)(Phen)(2)(H(2)O)(3)](dca).(phen) (Ln = Pr (1), Gd (2), and Sm (3), dca = N(CN)(-), phen = 1,10-phenanthroline) and [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n), (Ln = Gd (4), Sm (5), and La (6), 2,2'-bipy = 2,2'-bipydine), have been synthesized and structurally characterized by X-ray crystallography. The crystal structures of the first series (1-3) are isomorphous and consist of discrete [Ln(dca)(2)(Phen)(2)(H(2)O)(3)]+ cations, dca anions, and lattice phen molecules; whereas the structures of the second series (4-6) are characterized by infinite chains [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n). The Ln(III) atoms in all complexes are nine-coordinated and form a distorted tricapped trigonal prism environment. The three-dimensional frameworks of 1-6 are constructed by intermolecular hydrogen bond interactions. Variable-temperature magnetic susceptibility measurements for complexes 1, 2, 4, and 5 indicate a Curie-Weiss paramagnetic behavior over 5-300 K.

Five zinc complexes of T-shaped trans-1,2,3-propenetricarboxylic acid (H(3)L) with 1-D ribbon-like chain, 2-D rhombus-grid-like and herringbone-like layers, and non-interpenetrating 3-D open framework have been obtained based on different building blocks. X-ray single crystal analyses show that the T-shaped information of H(3)L was nicely expressed in the construction of herringbone-like or ladder-like structure. All compounds were found to display blue fluorescent emissions.