Synthesis,crystal structure,and luminescence properties of [TbGd(NAA)6(phen)2] and [Tb2(NNA)6(phen)2] · 2C3H7NO

Lanthanide(III) heteronuclear and binuclear complexes [TbGd(NAA)₆(phen)₂] (1) and [Tb₂(NAA)₆(phen)₂] · 2C₃H₇NO (2) (NAA = 1-naphthylacetic acid, phen = 1,10-phenanthroline) were prepared and their crystal structures were determined. In 1 and 2, each lanthanide is nine-coordinate by two bidentate-bridging and two tridentate chelating-bridging carboxylate groups, one bidentate chelating carboxylate and one phen molecule in a distorted monocapped square antiprism. The solid-state luminescence behavior and the antibacterial activities were studied. Complexes 1 and 2 exhibited characteristic emission of Tb(III) ion ⁵D₄ → ⁷F_J (J = 6–0) under UV radiation at room temperature. A main excitation peak (359 nm) of 2 appears under red emission of 615 nm. By contrast, all emission peak intensities of 1 were enhanced by addition of gadolinium(III), and the 545 nm band is much stronger than the 615 nm band, attributed to, under perturbation of the ligand field, the probability of ⁵D₄ → ⁷F₃ transition of Tb(III) was greatly enhanced in 2. Because of perturbation of the ligand field by addition of gadolinium(III), the probability of ⁵D₄ → ⁷F₅ transition of Tb(III) was greatly enhanced in 1 and green fluorescence was observed. The antibacterial activity showed that the two complexes were active against Escherichia coli, Staphylococcus aureus and Bacillus subtilis.     

Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

Complexes [Ca(H₂O)₂(Dmf@CB[6])(Bdc)] · DMF · 4H₂O (I) and [Ca(H₂O)₃(Dmf@CB[6])]Cl₂ · 2H₂O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H₂Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Synthesis, crystal structure and electrochemical property of 2D lamellar supermolecular complex [Cu(C6H4NO2)2 · H2O]

A 2D lamellar supermolecular complex [Cu(C₆H₄NO₂)₂ · H₂O] was synthesized and characterized by elementary analysis, infrared spectrum, ultraviolet spectrum, thermogravimetry analysis and crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, Pbca space group, with a = 1.2797(8), b = 1.2944(8), c = 1.4962(9) nm, Z = 8, V = 2.478(3) nm³, D _c = 1.746 g cm^?3, ?? = 1.784 mm^?1, F(000) = 1320, R ₁ = 0.0267, wR ₂ = 0.0762, GOOF = 1.015, which consists of a Cu(II) ion, two 2-Picolinic acid and a coordinated water molecule. The 5-coordinated geometry of the Cu cation is a distorted tetragonal-pyramidal configuration. The 1D chain structure is formed through hydrogen bonds O(w)-H??O between single cells, and the 2D lamellar supermolecular system is formed through the non-classical hydrogen bonds C-H??O between various chains. The complex displays a distinct absorption band (??_max = 648 nm) in aqueous solution. The electrochemical behavior shows a quasi-reversible course. (CCDC: 750880)     

Synthesis, crystal structure, and photophysical properties of acid (H3O)2[{W6Br8}Br6] · 4H2O

Compound (H₃O)₂[{W₆Br₈}Br₆] · 4H₂O is synthesized by the reaction of polymeric tungsten bromide W₆Br₁₂ with hydrobromic acid in an ethanolic solution. The structure of the compound is a packing of counterions H₃O⁺ and [{W₆Br₈}Br₆]^2? and crystallization water molecules joined with each other by an extended system of hydrogen bonds. The finely crystalline sample of the complex exhibits luminescence, whose spectrum has a broad profile from ??500 nm to more than 950 nm with a maximum at ??715 nm, with an absolute quantum yield of ??0.225. The emission is characterized by the biexponential decay with lifetimes of ??2.2 and ??8.4 ??s.     

Synthesis and properties of Na6[Pb(S2O3)4] · 6H2O

Conditions for the synthesis of the water-soluble lead thiosulfate complex Na₆[Pb(S₂O₃)₄] · 6H₂O were determined. The complex synthesized was characterized by UV and IR spectroscopy and X-ray phase and thermal analyses. Thermolysis schemes were proposed on the basis of the IR and mass spectra of the thermal decomposition products.     

Synthesis, crystal structure and magnetic properties of bimetallic complex of Ni2Co(TTHA)·12H2O

The bimetallic complex of Ni₂Co(TTHA)·12H₂O (TTHA = triethylene tetraminehexaacetic acid) was synthesized and characterized structurally and magnetically. The title complex crystallizes in the triclinic space group P ī with a = 0.7316(2), b = 0.8624(2), c = 1.5041(4) nm; α = 73.38(2), β = 83.97(2), γ = 70.50(2)°. The crystal structure is built up of [Ni₂(TTHA)(H₂O)₂]²⁻, Co(H₂O)₆²⁺ and water molecules. The variable magnetic measurement shows that there is strong antiferromagnetic interaction between two Ni(II) ions in [Ni₂(TTHA) (H₂O)₂]²⁻ with J _Ni−Ni = −141.64 cm⁻¹, g _Ni = 2.21 and that the constant of spin-orbit coupling of Co(II) ion is −134.8 cm⁻¹. __________ Translated from Acta Scientiarum Naturalium Universitatis Nankaiensis, 2007, 40(1): 6–10 [译自: 南开大学学报(自然科学版)]     

Synthesis, crystal structure, and thermal analysis of hexahydrogen dodecavanadate of composition [NH3 · H2O]6 · H6[Ca4V12O40] · 6H2O

Dihydrogen dodecavanadate of composition [NH₃ · H₂O]₆ · H₆[Ca₄V₁₂O₄₀] · 6H₂O was synthe-sized and studied by X-ray crystallography and TGA analyses. The crystals are cubic, space group I $\bar 4$ 3m;; unit cell parameters: a = 13.518(2) ?, V = 2470.4(3) ?³, ??_calc = 2.2334 g/cm³, Z = 2.     

Synthesis,crystal structure,and characterization of energetic complex Pb(ATZ)(phen)2 · 3H2O

A new energetic complex, Pb(ATZ)(phen)₂·3H₂O (1) (ATZ = 5,5′-azotetrazolate), was synthesized and characterized by single crystal X-ray diffraction. Crystal data: monoclinic, P2(1)/n space group, a = 8.4545(1) Å, b = 25.846(2)Å, c = 13.096(2)Å, and β = 102.873(2)°. In addition, elemental analysis, IR, and thermogravimetric analysis are presented. Furthermore, the complex was also explored as an additive to promote thermal decomposition of ammonium perchlorate.     

Synthesis and crystal structure of the complex [Mg(H2O)2(dmf@CB[6])(bdc)]·DMF·4H2O and the inclusion compound [dmf@CB[6]]·8H2O

The complex [Mg(H₂O)₂(dmf@CB[6])(bdc)]·DMF·4H₂O (1) and the inclusion compound [dmf@CB[6]]·8H₂O (2) were obtained from a mixture of magnesium perchlorate and water (for compound 1) or magnesium oxide and H₂SO₄ (for compound 2), and cucurbit[6]uryl (CB[6]) in the presence of N,N-dimethylformamide (DMF) with the additives of terephthalic or fumaric acid, respectively. X-ray diffraction studies showed that magnesium cation in compound 1 coordinated two oxygen atoms of the CB[6] molecule, one oxygen atom of the terephthalate anion, two molecules of water, and a DMF molecule located inside the cucurbit[6]uryl cavity. When fumaric acid was used instead of terephthalic acid under similar conditions of synthesis, no coordination of magnesium cations to cucurbit[6]uryl molecules took place, rather an inclusion compound of DMF into the macrocyclic cavitand was formed. Compounds 1 and 2 were characterized by X-ray diffraction data, IR spectroscopy, and elemental analysis.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

Synthesis,crystal structure modeling and thermal decomposition of yttrium propionate [Y2(CH3CH2COO)6·H2O]·3.5H2O

An yttrium propionate complex was synthesized and characterized for its application as precursor for Y₂O₃ based oxide thin films deposition and YBa₂Cu₃O_7 − x superconducting thin films. The TG–DTA and FT-IR analyses have revealed the formation of an yttrium propionate complex with the formula [Y₂(CH₃CH₂COO)₆·H₂O]·3.5H₂O. The molecular structure of the yttrium propionate complex was determined by modeling the FT-IR spectra. The coordination numbers for the yttrium ions are eight and nine, respectively being coordinated by bridging bimetallic triconnective and chelating bidentate propionate groups.The thermal decomposition of yttrium propionate has been investigated by thermogravimetric (TG) and differential thermal analysis (DTA) coupled with quadrupole mass spectrometry (QMS), X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques.     

Crystal structure and properties of H3[PMo12O40] · 3C2H6O

The title compound H₃[PMo₁₂O₄₀]· 3C₂H₆O was prepared and characterized by X-ray crystallography, its i.r. spectrum, cyclic voltammetry and e.s.r. spectra. The anion of the title compound is a Keggin-type heteropoly structure based upon a central PO₄ tetrahedron surrounded by 12 MoO₆ octahedra arranged in four groups of three edge-shared octahedra Mo₃O₁₃. Weak hydrogen bonds exist between the organic solvent molecules and the heteropoly anion. The catalytic activity of the title compound was determined by the synthesis of butyl acetate. The conversion of n-BuOH reached 93.3% and the yield of MeCO₂Bu-n was 92.0% when the ratio of MeCO₂H to n-BuOH, catalyst amount, reaction time, reaction temperature were 2:1, 0.24% of the reactants (50 mg), 2.0 h and 115 120 °C, respectively.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.     

A cyanide-containing cobalt(III) complex [Co(phen)2(CN)2][Co(phen)(CN)4]·4.5H2O: hydrothermal synthesis,crystal structure and spectroscopic properties

A cyanide-containing cobalt(III) complex, [Co(phen)₂(CN)₂][Co(phen)(CN)₄]?·?4.5H₂O (1: phen?=?1,10-phenanthroline) has been synthesized by hydrothermal techniques and characterized by elemental analyses, IR spectroscopy, UV–vis spectroscopy and single-crystal X-ray diffraction methods. The complex is triclinic, space group P 1 , with a?=?11.0047(16), b?=?12.9587(19), c?=?15.076(2)?Å, α?=?100.060(2), β?=?102.061(2), γ?=?91.803(2)°, V?=?2065.0(5)?ų, Z?=?2, and R ₁ [I?>?2σ(I)]?=?0.0481. The molecular unit of 1 consists of a cation/anion pair with interstitial water molecules in the crystal lattice. The combination of coordinative, hydrogen bonding and π–π stacking interactions results in the stabilization of a supramolecular solid-state architecture.     

Nonisothermal Kinetice of Dehydration Process of [Sm(m-CIBA)3phen]2·2H2O and[Sm(p-CIBA)3phen]2·2H2O

Compounds[Sm(m-CIBA)3phen]2·2H2O and[Sm(p-ClBA)3phen]2·2H2O(m-ClBA=m-chlorobenzoate,PClBA=p-chlorobenzoate,phen=1,10-phenanthroline)were prepared.The dehydration processes and kinetics of these compounds were studied from the analysis of the DSC curves using a method of processing the data of thermal analysis kinetics.The Arrhenius equation for the dehydration process can be expressed as lnk=38.65-243.90x103|RT for and△S≠ of dehydration reaction for the title compounds are determined,respectively.     

Preparation, characterization and crystal structure of Na4[Mn(NCS)6]·13H2O

Na₄[Mn(NCS)₆] · 13H₂O was prepared and characterized by chemical analysis, magnetic susceptibility, thermal dehydration reactions, and single crystal X-ray structure analysis. The crystals are triclinic with a=9.310(1)Å, b=9.367(1)Å, c=9.730(2)Å, = 89.89(1)°,=75.33(1)°, =70.72(1)°, space group P¯I.Z=1. The structure is built up from Na(H₂O)₅ S, Na(H₂O)₆, and Mn(NCS)₆, octahedra. All water molecules are coordinated to Na⁺ -ions in terminal as well as bridging fashion. They form O-H···O as well as O-H···S hydrogen bonds.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday