无机-有机杂化层状锑硫化合物的溶剂热合成与结构

用溶剂热法合成了有机杂化层状锑硫化合物[C3H7NH3]2Sb4S7,并利用单晶X-射线衍射测定了其晶体结构。该化合物为三斜晶系,Pī空间群。晶胞参数:a=7.0098(10),b=11.9710(14),c=13.6685(17),α=115.244(6)°,β=98.671(9)°,γ=92.413(13),°V=1018.3(2)3,Z=2,Mr=831.71 g.mol-1,(=5.984 mm-1,F(000)=772,偏差因子R1=0.0334,wR2=0.0766。该化合物由质子化正丙胺离子[C3H7NH3] 和二维阴离子[Sb4S7]n2n-组成,[Sb4S7]n2n-二维离子由3个SbS3三角锥和1个SbS4变形四面体单元连接而成,[C3H7NH3] 离子位于无机阴离子层之间,形成三明治夹心式结构,[C3H7NH3] 的-NH3 基团与无机阴离子层的S原子形成N-H…S氢键作用。     

Solvothermal synthesis and photoluminescent properties of ZnS/cyclohexylamine: inorganic-organic hybrid semiconductor nanowires

An inorganic-organic hybrid semiconductor, ZnS/CHA (CHA = cyclohexylamine) nanocomposites was successfully synthesized via a solvothermal method using CHA as solvent, which yielded uniform and ultralong nanowires with widths of 100-1000 nm and lengths of 5-20 microm. Changing the reaction conditions could alter the morphology and optical properties of the nanocomposites. The periodic layer subnanometer structures were identified by high-resolution transmission electron microscopy (HR-TEM) images, with thickness of approximately 2 nm. The composites exhibited a very large blue-shift in their optical absorption edge as well as an exciton excitation band due to a strong quantum confinement effect caused by the internal subnanometer-scale structures. The pure hexagonal wurtzite ZnS nanowires were also obtained by extracting the ZnS/CHA nanocomposites with dimethyl formamide (DMF). In addition, the luminescent properties of exciton and defect-related transitions in different samples of ZnS/CHA were discussed in detail.     

Solvothermal synthesis and structural characterization of a novel erbium(III)-carboxylate polymeric complex

A novel erbium(III)-carboxylate polymeric complex [{Er(H₂btec)_2/4(btec)_3/6(H₂O)}·2H₂O] _n , simplified as ECPC, (H₄btec=1,2,4,5-benzenetetracarboxylic acid) was synthesized under solvothermal conditions (H₂O/acetic acid). ECPC obtained was characterized by differential thermal analysis/thermogravimetry (DTA/TG), single-crystal X-ray diffraction, elemental analysis and FT-IR analysis techniques. The result of single-crystal X-ray diffraction analysis shows that the ECPC crystallizes in monoclinic symmetry, and the space group P2(1)/n, a=10.6933(15) Å, b=7.1243(10) Å, c=17.092(2) Å, α=γ=90°, β=97.109(2)°, V=1292.1(3) Å³, Z=4, R ₁=0.0286, wR ₂=0.0686. ECPC demonstrates a 3-D supramolecular framework containing nine-coordinate erbium centers and channels. The uncoordinated water molecules occupy the channels in ECPC. The results of TG/DTA, IR and elemental analysis performed also give positive information of the proposed crystal structure.     

A first transition series pseudotetrahedral oxynitride anion: synthesis and characterization of Ba(2)VO(3)N

Ammonolysis of reactive oxide precursors affords the vanadium(V) phase Ba(2)VO(3)N that is shown by X-ray and neutron powder diffraction and Raman spectroscopy to contain pseudotetrahedral VO(3)N(4-) anions. This is the first example of such species for the first transition series metals.     

Synthesis and structural characterization of a series of lanthanide(II) amides: steric effect of amido ligand

The synthesis and structures of a series of lanthanide(II) and lanthanide(III) complexes supported by the amido ligand N(SiMe3)Ar were described. Several lanthanide(III) amide chlorides were synthesized by a metathesis reaction of LnCl3 with lithium amide, including {[(C6H5)(Me3Si)N]2YbCl(THF)}2.PhCH3 (1), [(C6H3-iPr2-2,6)(SiMe3)N]2YbCl(mu-Cl)Li(THF)3.PhCH3 (4), [(C6H3-iPr2-2,6)(SiMe3)N]YbCl2(THF)3 (6), and [(C6H3-iPr2-2,6)(SiMe3)N]2SmCl3Li2(THF)4 (7). The reduction reaction of 1 with Na-K alloy afforded bisamide ytterbium(II) complex [(C6H5)(Me3Si)N]2Yb(DME)2 (2). The same reaction for Sm gave an insoluble black powder. An analogous samarium(II) complex [(C6H5)(Me3Si)N]2Sm(DME)2 (3) was prepared by the metathesis reaction of SmI2 with NaN(C6H5)(SiMe3). The reduction reaction of ytterbium chloride 4 with Na-K alloy afforded monoamide chloride {[(C6H3-iPr2-2,6)(SiMe3)N]Yb(mu-Cl)(THF)2}2 (5), which is the first example of ytterbium(II) amide chloride, formed via the cleavage of the Yb-N bond. The same reduction reaction of 7 gave a normal bisamide complex [(C6H3-iPr2-2,6)(SiMe3)N]2Sm(THF)2 (8) via Sm-Cl bond cleavage. This is the first example for the steric effect on the outcome of the reduction reaction in lanthanide(II) chemistry. 5 can also be synthesized by the Na/K alloy reduction reaction of 6. All of the complexes were fully characterized including X-ray diffraction for 1-7.     

Pectin based cerium (IV) and thorium (IV) phosphates as novel hybrid fibrous ion exchangers synthesis,characterization and thermal behaviour

Summary Pectin based cerium (IV) and thorium (IV) phosphates have been synthesized as new phases of hybrid fibrous ion exchangers. Both materials were characterized using X-ray diffraction, infrared (IR) spectra, thermogravimetric analysis (TG), differntial thermogravimetry (DTG), differntial thermal analysis (DTA) and scanning electron microscopy (SEM), as well as the determination of their ion exchange capacity, elution and pH titration. The X-ray study reveals the amorphous nature of the materials, while SEM studies confirm the fibrous nature of the materials. The thermal studies of these materials indicate that both of them are highly stable on heating as they retain about 97% of their ion-exchange capacity (i.e.c.) on heating up to 100°C and about 81% on heating up to 200°C.     

Microwave synthesis of hybrid inorganic-organic porous materials: phase-selective and rapid crystallization

Microwave synthesis of two porous nickel glutarates was compared with conventional hydrothermal synthesis. The cubic nickel glutarate, [Ni20(C5H6O4)20(H2O)8] x 40 H2O (1), was synthesized by conventional electrical heating in several hours or days, depending on synthesis temperature. Crystallization was greatly accelerated by microwave irradiation, in which more stable, tetragonal nickel glutarate, [Ni22(C5H6O4)20(OH)4(H2O)10] x 38 H2O (2), was formed within a few minutes, suggesting the efficiency of the microwave technique in the synthesis of porous hybrid materials. The cubic phase 1 is formed preferentially at low pH, low temperature, and especially under conventional electrical heating. In contrast, the tetragonal phase 2 is obtained favorably at high pH, high temperature, and especially with microwave irradiation. This work demonstrates that the microwave method provides not only the very fast synthesis of a hybrid material, but also the possibility to discover a new porous hybrid material not yet identified by conventional hydrothermal synthesis. The hydrothermal formation of metal-organic hybrid materials in a matter of minutes is an important step towards developing commercially viable routes for producing this valuable class of materials.     

Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-membered cyclic dithiocarbamates

Abstract

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and tri-cyclohexyltin: [(C₄H₉)₂Sn{S₂CN(CH₂)₆}₂] (3), [(C₆H₁₁)₃Sn{S₂CN(CH₂)₆}] (4), and [(C₆H₁₁)₃Sn}₂ (μ-S₂CN(C₅H₁₀)NCS₂)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, and were characterized by elemental analyses, IR, FAB⁺–MS, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray diffraction studies. The geometrical arrangement around the tin atom can be described as distorted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithiocarbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while (3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally neighboring molecule, giving rise to a zig-zag polymeric structure.     

Two tetrakis(benzoylacetonato)lanthanide species: synthesis,characterization and structures of tetrakis(benzoylacetonato)cerium(IV) and triethylammonium tetrakis(benzoylacetonato)lanthanate(III) tetrahydrate

Tetrakis(benzoylacetonato)cerium(IV), [Ce(bzac)₄] and triethylammonium tetrakis(benzoylacetonato)lanthanate(III) tetrahydrate, [Et₃NH][La(bzac)₄] · 4H₂O were prepared and characterized by TG and DCS measurements, IR spectroscopy, and X-ray structure analysis. The coordination polyhedron of cerium is a trigonal dodecahedron, while that of lanthanum is a distorted square antiprism. Thermal and spectroscopic measurements indicate that bonding of the ligand to metal is stronger in [Ce(bzac)₄] than in [La(bzac)₄]^?.     

Tin(IV) cyanoximates: synthesis, characterization, and cytotoxicity

In recent years, numerous organotin(IV) derivatives have exhibited remarkable cytotoxicity against several types of cancer. However, the properties of the cyanoxime-containing organotin(IV) complexes are unknown. Previously, it has been shown that cyanoximes displayed an interesting spectrum of biological activity ranging from growth-regulation to antimicrobial and pesticide detoxification actions. The work presented here attempts to combine the useful properties of both groups of compounds and investigate the likely antiproliferating activity of the new substances. A series of 19 organotin(IV) complexes, with nine different cyanoxime ligands, were anaerobically prepared by means of the heterogeneous metathesis reaction between the respective organotin(IV) halides (Cl, Br) and ML (M=Ag, Tl; L=cyanoximate anion), using an ultrasound in the CH3CN at room temperature. The compounds were characterized using spectroscopic methods (UV-visible, IR, 1H,13C NMR, 119Sn M?ssbauer) and X-ray analysis. The crystal structures of the complexes revealed the formation of two types of tin(IV) cyanoximates: mononuclear five-coordinated compounds of R4-xSnLx composition (R=Me, Et, n-Bu, Ph; x=1, 2; L=cyanoximate anion), and the tetranuclear R8Sn4(OH)2O2L2 species (R=n-Bu, Ph). The latter complex contains a planar [Sn4(OH)2O2]2- core, consisting of three adjacent rhombs with bridging oxo and hydroxo groups. The tin(IV) atoms are five-coordinated and have distorted trigonal-pyramidal surrounding. This is the first instance when the organic anions were found to act as monodentate O-bound planar oxime ligands. All of the compounds were studied in vitro for antiproliferating activity, using human cervical cancer HeLa and WiDR colon cancer cell lines; cisplatin was used as a positive control substance. The two dibutyltin(IV) cyanoximates showed cytotoxicity similar and greater to that of cisplatin.     

The first examples of lanthanide selenite-carboxylate compounds: syntheses, crystal structures and properties

[Ln(8)(SeO(3))(4)(2,6-pdc)(8)(H(2)O)(10)].2H(2)O (Ln = La (1), Nd (2), Eu (3); 2,6-pdcH(2) = pyridine-2,6-dicarboxylic acid) represent the first examples of luminescent lanthanide selenite-carboxylate compounds. The compounds have been hydrothermally synthesized and structurally characterized. The structures feature two-dimensional (2D) host frameworks composed of Ln(8)(SeO(3))(4)(2,6-pdc)(8)(H(2)O)(10) clusters connected to each other via inter-cluster Ln(2)O(2) rhombic units along the b-axis and 12-membered Ln(4)O(2)(COO)(2) rings along the c-axis. Inter-layer H-bonding interactions between coordinated water molecules and carboxylate groups lead to three-dimensional architectures. Thermogravimetric analysis (TGA) indicated that the 2D networks were thermostable up to approximately 450 degrees C after losing both coordinated and lattice water molecules and underwent reversible process of dehydration and rehydration. Study on photoluminescent properties revealed that compounds 1, 2 and 3 were new rare-earth materials with violet, near-infrared, and red luminescence, respectively.     

New methacrylate-functionalized ba and ba-ti oxoclusters as potential nanosized building blocks for inorganic-organic hybrid materials: synthesis and characterization

Two different methacrylate modified barium-titanium and barium-based oxoclusters, Ba2Ti10(mu3-O)8(mu2-OH)5(mu2-OMc)20(OiPrOMe)2 (1) and [Ba(OMc)2(McOH)3]n (2), were synthesized by reacting methacrylic acid with barium-titanium and barium-zirconium double alkoxides, respectively. The X-ray structure determination of oxocluster 1 shows a core consisting of a ring of 10 titania octahedra, sharing corners, that surround the two barium oxygen decaeders which are linked by common edges to the titania octahedra and the neighboring barium decaeder. The solid-state structure of 2 consists of zigzag chains of edge-sharing {BaO9} polyhedra linked through bridging bidentate metacrylate anions, displaying different coordination mode of carboxylate groups. The presence of methacrylate groups surrounding the two polynuclear compounds has been exploited for the embedding of the oxocluster in inorganic-organic hybrid materials, and some preliminary results are presented.     

Preparation and characterization of novel inorganic-organic hybrid materials containing rare, mixed-halide anions of bismuth(III)

Three new hybrid inorganic-organic salts containing novel mixed haloanions of bismuth were synthesized by the solvothermal reaction of bismuth iodide with a haloacid, HX (X = Cl or Br), and the alkylamine 4,4'-trimethylenedipiperidine (TMDP). All three compounds were structurally characterized by single-crystal X-ray diffraction. Reaction of TMDP and BiI(3) with HCl yielded two crystalline products: [H(2)TMDP](2)[(Bi(2)I(9))(BiCl(2)I(2))] (1, major yield) and [H(2)TMDP](2)[Bi(2)Cl(10-x)I(x)] (2, x = 3.83, minor yield). Compound 1 crystallizes in the monoclinic space group Cc (a = 22.8586(11) A, b = 15.5878(7) A, c = 17.6793(9) A, beta = 118.7010(10) degrees , Z = 4) and contains the mononuclear mixed-halide anion BiCl(2)I(2)(-) in addition to a face-sharing bioctahedral Bi(2)I(9)(3)(-) anion and two independent H(2)TMDP(2+) cations. The BiCl(2)I(2)(-) anion has a sawhorse geometry (equatorially vacant trigonal bipyramidal geometry) that is not commonly observed in bismuth chemistry. Compound 2 crystallizes in the monoclinic space group P2(1)/c (a = 14.9471(7) A, b = 12.7622(6) A, c = 13.3381(7) A, beta = 116.1030(10) degrees , Z = 2) and contains an edge-sharing bioctahedral mixed-halide anion in which iodide occupies one and chloride occupies two of the five crystallographically independent halide sites. The remaining two sites have mixed-chloride and -iodide occupancy. Reaction of TMDP and BiI(3) with HBr yielded the crystalline product [H(2)TMDP][BiBr(5-x)I(x)] (3, x = 0.99), which contains, in addition to the organic cation, a polymeric, mixed-haloanion of bismuth(III). Compound 3 crystallizes in the chiral, orthorhombic space group P2(1)2(1)2(1) (a = 8.5189(5) A, b = 14.8988(9) A, c = 17.9984(11) A, Z = 4) and consists of an H(2)TMDP(2+) cation in addition to the anion, which is built up of corner-sharing BiX(6) octahedra. Of the five crystallographically independent halide sites in this anion, two are occupied solely by Br and the remaining three have mixed-bromide and -iodide occupancy. Other anion stoichiometries have been observed crystallographically for 3, as the specific stoichiometry is dependent on the relative concentration of the haloacid starting material used.     

Framework-substituted lanthanide MCM-22 zeolite: synthesis and characterization

Incorporation of Ce and La into the framework of MCM-22 zeolite has been achieved by cohydrolysis and condensation of tetraethylorthosilicate and lanthanide salts in moderate/weak acidic media followed by a switch of synthesis gels to basic conditions for hydrothermal crystallization. The promotion effect of the framework Ce (La) when Ce(La)-MCM-22 serves as the catalyst support for hydroisomerization of n-heptane is demonstrated. Framework substitutions of lanthanides are evidenced by a set of mutually complementary characterizations, catalytic tests, and item-by-item comparisons with the impregnated and ion-exchanged counterparts. The novel synthesis strategy may give further outlines for the production of other types of heteroatomic zeolites.     

Synthesis of the first examples of stable heterometallic isopropoxides of an organometallic RSn(IV) moiety

Five-, six-, and seven-coordinate volatile butyltin(IV) heterobimetallic derivatives, respectively of the types, [BuSn{(μ-OPrⁱ)₂Al(OPrⁱ)₂}Cl₂] (1), [BuSn{(μ-OPrⁱ)₂Al(OPrⁱ)₂}₂Cl] (2), and BuSn{(μ-OPrⁱ)₂M(OPrⁱ)_x − 2}₃ (3:M = Al (x = 4); 4:M = Ga (x = 4); 5:M = Nb (x = 6)) have been synthesized by the reactions of BuSnCl₃ with potassium tetraisopropoxoaluminate in 1:1, 1:2, and 1:3 molar ratios. Replacement reactions of chloride in (1) and (2) with appropriate alkoxometallate (tetraisopropoxoaluminate, tetraisopropoxogallate, or hexaisopropoxoniobate) ligands result in the formation of novel BuSn(IV) heterotri- and tetra-metallic derivatives. All of these derivatives have been characterized by elemental analyses, molecular weight measurements, and spectroscopic (IR, ¹H, ²⁷Al, and ¹¹⁹Sn NMR) studies. Based on these studies, plausible structures for the new derivatives involving bidentate ligation of the alkoxometallate ligands have been suggested.     

The synthesis,characterization and reactions of a binuclear tetramethylplatinum(IV) complex

Reaction of excess MeLi and MeI with [PtCl₂SMe₂)₂] gives the first binuclear tetramethylplatinum(IV) complex [Pt₂Me₈(μ-SMe₂)₂]. The characterization of this complex, and its reactions with donor ligands to give cis-[PtMe₄L₂] (L₂ = Ph₂PCH₂PPh₂, Ph₂PCH₂CH₂PPh₂, 2,2′-bipyridyl, 1,10-phenanthroline or L = PMe₂Ph, PMePh₂) are described.     

Silver(I) arylsulfonates: a systematic study of "softer" hybrid inorganic-organic solids

The present study represents the first systematic examination of the effects on the layered structure of simple silver aryl-monosulfonates as the breadth of the pendant aryl group is increased beyond that where a simple "phosphonate-like" motif is sustainable. Five new silver arenesulfonates are reported. On the basis of comparison with Ag benzenesulfonate, a threshold of approximately 6.4 A is proposed and confirmed as the critical breadth of an aryl group for a simple layered motif to be observed in silver sulfonates. Ag 1,1'-biphenyl-4-sulfonate (1) and Ag 2-naphthalenesulfonate (2) are below this threshold and so form simple layered networks, termed type 1 solids. When the pendant group is broadened to a 1-naphthyl group, the layer incorporates coordinated water to maintain a layered structure giving Ag 1-naphthalenesulfonate hemihydrate (3a). This more diffuse structure is termed a type 2 solid. For anhydrous Ag 1-naphthalenesulfonate (3) and Ag 1-pyrenesulfonate (4), the additional breadth is compensated for by the formation of Ag-pi interactions and the formation of type 3 solids. Interactions between the pendant groups are observed to play a significant role in the packing of the solid. All frameworks are characterized by single crystal and powder X-ray diffraction, IR, DSC-TGA, and elemental analysis. The significance of this adaptable framework is discussed along with implications for design of stacked arene arrays.     

Synthesis, characterization, and cytotoxicity of a series of estrogen-tethered platinum(IV) complexes

Several estrogen-tethered platinum(IV) complexes were prepared and characterized by ESI-MS and (1)H NMR spectroscopy. Their design was inspired by the observation that estrogen receptor-positive cells exposed to the hormone are sensitized to cisplatin. Intracellular reduction of bis-estrogen-cis-diamminedichloroplatinum(IV), BEP(n) (where n = 1-5 methylene groups between Pt and estrogen), occurs to afford cisplatin and two equivalents of the linker-modified estrogen. The ability of BEP(n) to induce overexpression of HMGB1 was established by immunofluorescence microscopy. The cytotoxicity of the compounds was evaluated in ER(+) MCF-7 and ER(-) HCC-1937 human breast cancer cell lines. BEP3 selectively induces overexpression of HMGB1 in MCF-7 cells, compared to HCC-1937 cells, and enhances their sensitivity (IC(50) = 2.1 +/- 0.4 microM versus 3.7 +/- 0.9 microM, respectively) to the compound. The difference in compound activities and the potential of compounds of this class for treating breast and ovarian cancer are discussed.     

Organotin(IV) complexes of thiohydrazones: synthesis, characterization and antifungal study

Some new organotin(IV) complexes with salicylaldehyde aniline-N-thiohydrazone (L1) and cinamaldehyde aniline-N-thiohydrazone (L2) of the type (p-ClC6H4)3Sn[L] Cl and (p-ClC6H4)2Sn[L]Cl2 have been synthesized (where L = L1 and L2). The complexes and ligands were characterized by elemental analysis and spectral (UV-vis, IR and 1H NMR) studies. In all the complexes, ligands act as bidentate, coordination through sulphur and azomethane nitrogen. Complexes are 1:1 metal ligands complexes. Antifungal studies of some complexes against Rhizoctonia bataticola fungal strain have been carried out.