One Novel Mn(Ⅱ) Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn(II) complex, [Mn(pmta)_3]_2[Mn(H_2O)_6]·4H_2O(1), is reported(Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid). In the title compound, the asymmetric unit consists of a [Mn(pmta_)3]ˉ anion, half [Mn(H_2O)_6]~(2+) counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

Synthesis,Structure and Near-infrared Photoluminescent Property of a Tetranuclear Er(Ⅲ) Complex

A tetranuclear erbium complex with pyridine-2,4,6-tricarboxylic acid(H3ptc), [Er4(ptc)4(H2O)18]·6H2O(1), has been synthesized by hydrothermal method. The complex crystallizes in triclinic system, space group P1, with a = 7.620(2), b = 10.459(3), c = 17.418(5) ?, α = 92.351(5), β = 92.080(5), γ = 95.627(4)°, V = 1379.1(7) ?3 and Z = 2. One Er(III) cation is eight-coordinated and the other is nine-coordinated. The complex exhibits characteristic luminescence of erbium cation in near-infrared region upon the excitation of UV-rays. Furthermore, a three-dimensional supramolecular complex was formed by weak hydrogen bonds among the tetranuclear units.     

Syntheses and Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO_4)_2(L = 1,4,8,11-tetraazacyclotetradecane) with NH_4VO_3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO_3]_2·2.33H_2O(1), [CuL]_3[V_(10)O_(28)]·8H_2O(2) and [Cu L]3[V_6O_(18)]·8H_2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V_6O_(18)]6- ring, [V_(10)O_(28)]6- cluster, and [V_(12)O_(35)]~(10-) ring, were isolated from the same reactant NH_4VO_3 under different conditions. The [CuL]~(2+) bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V_6O_(18)]~(6-) rings in 1 and [V_(12)O_(35)]~(10-) rings in 3 into three-dimensional frameworks, respectively.     

Synthesis,crystal structure,magnetic properties and second harmonic generation of a new noncentrosymmetric coordination compound:Triaqua(4-amino-6-methoxypyrimidine) cuprate(Ⅱ)sulfate

The chemical preparation, crystal structure and infrared spectroscopic characterization of the triaqua(4-amino-6-methoxypyrimidine) cuprate(II) sulfate, [Cu(C_5H_7N_3)(H_2O)_3]SO_4, is reported. The compound crystallizes in the noncentrosymmetric orthorhombic space group P2_12_12_1 with lattice parameters a = 7.9025(3), b = 11.1189(4), c = 12.9720(4) , V = 1139.81(7) ~3 and Z = 4. The Cu(II) cation is fivecoordinated, in an early half-way between square pyramidal and trigonal bipyramidal fashion, by two nitrogen atoms of the 4-amino-6-methoxypyrimidine ligand and three water oxygen atoms. In the atomic arrangement, the organic ligands and the 5-connected Cu centers are linked with each other to give a 1-D corrugated hybrid chain running along the b-axis direction. The chains are interconnected by the SO_4~(2-) anions via O–H...O, O–H...S, C–H...O and N–H...O hydrogen bonds to form layers spreading parallel to the(011) plane. The vibrational absorption bands were identified by infrared spectroscopy. Quantitative measurements of the second harmonic generation(SHG) of a powdered sample at 1064 nm were performed and a relative efficiency of 5.2 times the KDP standard was observed. Magnetic properties were also defined to characterize the complex. Magnetic measurements revealed that this material had a onedimensional antiferromagnetic character. The magnetic parameters were g = 2.11 and 2J/k B = -36 K.     

Studies on the Interaction of Cobalt Mixed-Ligand Coordination Compound Containing Tetrapyrido [3,2-a:2′,3′-c:3″, 2″-h:2■,3■-j] phenazine with DNA

A new monometallic complex [Co(phen)_2tpphz]~(3+) (where tpphz is tetrapyrido [3,2-a:2′,3′-c:3″,2″-h:2′″,3′″-j] phenazine) was synthesized by the reaction of 5, 6-diamino-1,10-phenanthroline with [Co(phen)_2(phendione)]~(3+). It was characterized by elemental analysis, molar conductivity, IR, ~1H NMR, ultraviolet and fluorescence spectroscopy. The interaction of the complex with DNA was also investigated. The complex shows the absorption hypochromicity, fluorescence enhancement, the specific viscosity increased when bound to calf thymus DNA. The cyclic voltammetry (CV) measurement showed a change in peak current with the addition of DNA. All the results provide the support for the intercalative binding mode of the mononuclear complex.     

Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

SYNTHESIS AND STRUCTURE OF A TRITHIOCARBONATO Mo(Et_4 N)_2 [(S_2)Mo_2O_2(μ-S)_2(CS_3)]

A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from asystem containing MoO_4~(2-),S_x~(2-),and CS_2 and characterized by IR and X-ray structural analysis.The complex crystallizes in the (?)onoclinic space group P2_1/c with a=9.539(3)(?),b=20.745(2)(?),c=15.452(2)(?),β=94.58(2)°,and Z=4.The structure was solved by direct anddifference Fourier synthesis methods.Least squares refinement using 2910 reflections withI>3σ(I)converged to R=0.054.The CS_3~(2-) iigand in the complex chelates to Mo atom andvalues of the C-S bond distances in the CS_3~(2-) ligend indicate a substantial contribution ofthree resonance forms.     

Synthesis, Structure and Luminescence of Zn4.5Cu3 Heteronuclear Coordination Polymer Comprising Macrocyclic Oxamide and 5-Sulfosalicylic Ion

<正>The complex[Zn_(4.5)(SSA)_3(CuL)_3(H_2O)_6]_n was synthesized and structurally determined,where SSA is fully deprotonated 5-sulfosalicylic acid(CuL,H_2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca- 7,13-dien).The title complex crystallized in the triclinic system with space group P1,a=1.19788(17) nm,b=1.4253(2) nm,c=2.2890(4) nm,α=90.211(2)°,β=93.076(2)°,γ=90.600(2)°.The complex displayed a 1D ladderlike chain.All these 1D chains were further interlinked via hydrogen bonds,resulting in a 2D architecture.The luminescent property of the compound was also discussed.     

Spectroelectrochemical studies of [Mo(dtc)_4][Eu(dtc)_4] and [Mo(dtc)_4][Er(dtc)_4]

Redox and spectroscopic properties of the eight-coordination complexes of molybdenum and the rare-earth elements Eu or Er with N,N-diethyldithiocarbamate (dtc) were characterised by cyclic voltamrnetry and UV-visible absorption spectra.The complex cation [Mo(dtc)4]+ is more stable than the complex anions [Eu(dtc)4]-and [Er(dtc)4]-in redox processes,and possesses good redox reversibility.The electron transfer number,formal standard electrode potential in the redox process for the complex cation and its diffusion coefficients were obtained by in aitu spectroelectro-chemistry.     

SYNTHESIS, MAGNETIC PROPERTY AND X-RAY CRYSTAL STUCTURE OF MIXED VALENT COBALT COMPLEX SALT [Co~Ⅲ Cl_2(py)_4][Co~Ⅱ Cl_3(py)]

Complex salt Co_2Cl_5(py)_5 (py=pyridine) was obtained by the reaction of CoCl_2·6H_2O with Bu_4NMnO_4 in pyridine in the presence of benzoic acid. It is monoclinic and crystallizes in space group P2_1/n, fw=690.64, a=28.652(5), b=14.108(4), c=7.424(3) ;β=90.09(1); V=3001(2)~3; Z=4, Dc=1.53g/cm~3. Final R factor is 0.041. The structure consists of a discrete cation [Co~ⅢCl_2(py)_4]~+ and an anion [Co~Ⅱ Cl_3(py)]~-. The Co~Ⅲ ion is coordinated by two Cl~- and four pyridine nitrogen atoms to form an octahedral geometry, and Co~Ⅱ is coordinated by three Cl~- and one pyridine nitrogen atom to form the apices of a tetrahedron. The variable-temperature magnetic susceptility measurement shows no magnet-exchange interaction between Co~Ⅲ and Co~Ⅱ ions.     

Syntheses,Structures,Fluorescence and Heterogeneous Catalysis of Coordination Polymers with 4-Benzoimidazol-1-yl-methyl Benzoic Acid and 2,2′-Dipyridine

Two coordination polymers called [Ni(L)_2]_n(1) and [Ni(2,2?-bpy)_22(H_2O)]n (2)(HL = 4-benzoimidazol-1-yl-methyl benzoic acid, 2,2?-bpy = 2,2?-dipyridine) were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P2_1/c with a = 14.673(3), b = 10.773(2), c = 16.566(3) ?, V = 2559.2(8) ?~3, Z = 4 and F(000) = 1160. 2 also crystallizes in monoclinic system, space group C2/c with a = 15.404(3), b = 12.652(3), c = 6.5362(13) ?, V = 1246.2(5) ?~3, Z = 4 and F(000) = 712. The bridging L ligand connects the Ni~Ⅱ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO_4~(2-) ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.     

Synthesis,Crystal Structure and Spectroscopy Studies on Complex cis-Os~Ⅱ(bpy)_2Cl_2 and Its Oxidation Product [cis-Os~Ⅲ(bpy)_2Cl_2](PF_6)

The treatment of(NH_4)_2 OsCl_6 with 2 equiv of bpy in ethylene glycol produced complex 1, cis-Os~Ⅱ(bpy)_2Cl_2(bpy = 2,2?-bipyridine). Its one-electron oxidation product 2, [cis-Os~Ⅲ-(bpy)_2Cl_2](PF_6), was obtained by the oxidation of 1 with(Cp)_2 FePF_6. Complex 1 crystallizes in the orthorhombic space group Pbca, and adopts distorted [MCl_2 N_4] octahedral coordination, in which four coordination sites are occupied by four nitrogen atoms from two bpy ligands and the other two sites are occupied by two chlorine atoms in a cis-position. Complex 2 crystallizes in monoclinic space group C2/c, and contains one [Os(bpy)_2Cl_2]~+ cation, one PF_6~- anion and two uncoordinated water solvent molecules.     

CRYSTAL STRUCTURE OF [Ce~(Ⅲ)Cl_2(THF)_5][Ce~ⅣC15(THF)]

<正> INTRODUCTION. The attempt to prepare C_9H_7CeCl_2. nTHF(C_9H_7=indenyl) by the reaction of CeCl_4 3THF with C_9H_7Na in THF(tetrahydrofuran) has failed, but an unexpected orange crystal was obtained and determined by single cryntal X-ray diffraction to be a new complex [Ce~ⅢCl_2 (THF)_5]~+[Ce~ⅣCl_5 THF]~-. The valence state of the cerium atom in the cation is different from that in the anion, the former being trivalent while the latter quadrivalent. In this paper the crystal structure of the new complex is reported.     

Structural Regularities of the Transition Metal Complexes Containing o-Benzenedithiol (H_2bdt)——Synthesis and Structure of Fe_3(bdt)_3(PBu_3~n)_3

Complex Fe_3(bdt)_3(PBu_3~n)_3 was synthesized in the presence of PBu_3~n and the structural regularities in a series of transition metal complexes containing bdtH_2 ligand were summarized. The title complex crystallizes in the triclinic space group P-, Mr=1195.19, cell parameters: a=13.283(3), b=20.115(5), c=13.156(3), (?)=90.33(2), β= 116.47 (1), γ=92.19(2)°, V=3143.5(2.7)~3, Z=2, d_c=1.26g/cm~3. The structure was solved by direct methods from 4122 unique reflections with I>4σ(I) and reached the final convergence factor of R(Rw) = 0.053 (0.060). The complex exhibits strong paramagnetism.     

THE STATE OF CHROMIUM (Ⅲ) ION IN AQUEOUS SOLUTION

So far few systematic studies on the hydrolytic polymerization of Cr(Ⅲ) were reported because of inertness of the ion and complication of the process. We studied it in equilibrium by pH method systematically in a wide concentration range (0.0002—0.32 M). The results show that, in the low concentration range, the composition of the polynuclear hydrolysis products may be represented as [Cr_3(OH)_4] (OH)_n (n=1,2,3); in the medium range, the composition of products as Cr[Cr(OH)_2]_n~((3+n))~+ (n=1,2,3); in the high range, the composition of products as Cr[Gr(OH)]_n~((3+2n))~+ (n=1, 2), and in the intermediate range between medium and high range where the hydrolysis system is in a transition state, the composition of products as [Cr_3(OH)_3]~(6+) and [Cr_3(OH)_4]~(5+). The values of hydrolysis constants of the identical species measured in different Cr concentration ranges and calculated by different methods were found in good agreement with each other. A predominance-arca diagram was made by using the hy     

Synthesis,Crystal Structure and Photoluminescence of a TADF Dinuclear Cu(Ⅰ) Complex

A binuclear Cu(Ⅰ) complex[Cu(PCNP)(mepypz)]_2(BF_4)_2 (1,PCNP=2,6-bis(diphenylphosphine)-benzonitrile,mepypz=2-methyl-6-(1H-pyrazol-3-yl)-pyridine was synthesized from the reaction of Cu(CH_3CN)_4BF_4,PCNP and mepypz in CH_2Cl_2 at room temperature.The compound was characterized by NMR,UV-vis and X-ray single-crystal structure analysis.It crystallizes in monoclinic space group P2_1/c with a=14.0139(5),b=11.8149(3),c=27.1248(10)?,β=96.686(4)°,V=4460.6(3)?~3,Z=2,M_r=1561.97,D_c=1.163 g/cm~3,F(000)=1600.0,μ=1.774 mm~(–1),GOOF=1.071,the final R=0.0523 and w R=0.1412 for 7919 observed reflections with I2σ(I).The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry.In the solid state,the complex exhibits yellowish-green emission with a peak wavelength of 546 nm,a lifetime of 390μs,and a quantum yield of 0.45 at room temperature.The temperature-dependent investigation of luminescent properties suggests that the complex emits thermally activated delayed fluorescence (TADF) at room temperature.     

Synthesis,Crystal Structure and Photoluminescence of a Dinuclear Cuprous Complex with Thiocyanate Bridges

A cuprous dinuclear copper complex [PPh_2PAr_2Cu(μ-SCN)_2CuPPh_2PAr_2](1,PPh_2PAr_2 =(1-bis(2-methylphenyl)-phosphine-2-diphenylphosphino)benzene) was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225(2),b = 11.360(2),c = 13.420(3) ?,α = 95.81(3),β = 93.45(3),γ = 113.78(3)°,V = 1410.4(5) ?~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm~3,F(000) = 616,μ = 3.029 mm~(–1),GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu(I) is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu(μ-SCN)_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_(max)= 478 nm(1),lifetimes 4.7 μs and quantum yields(ф = 0.43) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ~(1,3)MLCT excited states.     

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl) Ether: Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis(2-dimethylaminoethyl) ether(BDMAE) with nickel acetate afforded a novel 3D nickel(Ⅱ) complex [Ni(BDMAE)(H_2O)_3·(CH_3COO)_2·(H_2O)_2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823(2), b=13.932(3), c=17.563(4) ?, V=2158.9(8) ?~3, Z=4, C_(12)H_(36)N_2NiO_(10), Mr=427.14, Dc=1.314 g/cm~3, F(000)=920 and μ=0.944 mm~(-1). Single-crystal X-ray diffraction reveals that the mononuclear nickel(Ⅱ) ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.     

INVESTIGATION ON SYNTHESIS, STRUCTURE AND PROPERTIES OF THE CLUSTER COMPLEX,[(MoS_4)Fe(MoS_4O)] [(C_4H_9)_4N]_3

In this paper, we report a new Mo-Fe-S cluster complex containing an oxygen ligand. Itwas synthesized by the reaction of (NH_4)_2 MoS_4, FeCl_3 in the solution of sodium glycol. The chemical formula of the crystal, [(MoS_4) Fe (MoS_4O)] [(C_4H_9)_4N]_3, was characterized byX-ray. This complex was determined by IR, UV/Vis and Mossbauer spectra as well. The re-suits from Mossbauer spectra of the complex show an isomer shift, δ_m = 0.2263mm/s and aquadrupole splitting, E_q = 0.4527mm/s. The complex has some activity for the reduetion of aectylene to ethylene in the presenceof KBH_4.