二正丁基二硫代氨基甲酸锌配合物的量子化学研究

The geometric configurations of binuclear Zinc(Ⅱ) complex Zn₂[(n-Bu)₂NCSS]₄ and the ligand Na[(n-Bu)₂ NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G^* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π^* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π^* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS₂ and to increase the energy needed for the π → π^* and n → π^* transitions, and results in the absorption bands shifting towards the short wavelength direction.     

“风车状”双核镉配合物[Cd2(3-PyOH)4(FBA)4]的合成、晶体结构及热稳定性

A dinuclear cadmium complex, [Cd₂(3-PyOH)₄(FBA)₄] (FBA^-=4-formylbenzoate monoanion, C₈H₅O₃, 3-PyOH=3-hydroxypyridine), was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction. Each cadmium(II) ion is six-coordinated by four O atoms from three different FBA^- groups and two N atoms from two different 3-PyOH ligands, giving a distorted octahedral geometry. The two cadmium(II) atoms are bridged by two FBA- groups, with the Cd…Cd distances being 0.392 8(6) nm. In addition, there are two kinds of π-π stacking interactions between the two adjacent parallel 3-PyOH ligands in the title complex, with the Cg…Cg (Cg is the centroid of the above rings) distances of 0.361 0(5) and 0.385 2(6) nm, respectively. A two-dimensional supramolecular layer structure is constructed by intermolecular hydrogen bonds between the carboxyl O atoms of the FBA^- groups and the 3-PyOH ligands in ab plane. CCDC: 619649.     

链状螺旋配位聚合物[Zn(BBP)(p-CPOA)]n的合成及表征

A coordination polymer of [Zn(BBP)(p-CPOA)]_n(where BBP is 2，6-bis(benzimidazolyl)pyridine and p-CPOA is p-carboxylato-phenoxyacetate dianion) has been synthesized and characterized by elemental analysis， IR， TG， and the single crystal structure was determined by X-ray diffraction. The crystal crystallizes in the monoclinic system， space group of P2₁/n with a=1.397 3(4) nm， b=1.138 4(3) nm， c=1.575 9(5) nm， β=91.805(1)°， V=2.505 4(13) nm³， Z=4， D_c=1.513 g·cm^-3， μ=1.030 mm^-1 and F(000)=1 168. Zn(Ⅱ) ion is penta-coordinated and surrounded by two carboxylate O atoms from two different p-CPOA groups in a bis-monodentate mode， three N atoms from the 2，6-bis(benzimidazolyl)pyridine ligand， completing a distorted trigonal bipyramidal coordination configuration. The structure is a helix with a long pitch of 1.138 4 nm. Under direction of supramolecular recognition and attraction， the adjacent chains are formed the double-stranded chain through π-π stacking between the 2，6-bis(benzimidazolyl)pyridine ligands and hydrogen-bonding interactions. A three-dimensional supramolecular network is further constructed through these interactions between the helices. The TG shows that its chain skeleton is thermally stable up to 382 ℃. CCDC: 626650.     

锌与邻菲咯啉和α-萘乙酸配合物的合成、结构和抗菌活性

The complex with the molecular formula of Zn(Phen)(NAA)₂ was synthesized by the reaction of ZnSO₄, naphthylacetic acid and phenanthroline in ethanol-water solution at about pH≈7. It was characterized by elemental analysis, IR spectrum and X-ray single crystal diffraction. The antibacterial activity on E. Coli, S. Aureus and B. Subtilis were also been studied. The crystal of the complex belongs to triclinic system with space group P1, a=1.300 2 nm, b=1.306 4 nm, c=1.714 4 nm, α=89.41°, β=77.06°, γ=86.70°, V=2.833 5(2) nm³, Z=4, D_c=1.444 g·cm^-3, M_r=615.96, μ(Mo Kα)=0.912 mm^-1, the final R=0.039 8 and wR=0.103 4 [I>2σ(I)], F(000)=1 272. An asymmetry unit is composed of two independent molecules of Zn(Phen)(NAA)₂ with different bond length and bond angles. There exist two kinds of face to face π-π stacking interactions . The complex has a good effect against E. Coli. CCDC: 619222.     

一维链状镉(Ⅱ)配位聚合物{[Cd(PAc)2(4，4′-bipy)(H2O)]·4H2O}n的合成、晶体结构及热稳定性研究

A novel one-dimensional coordination polymer, {[Cd(PAc)₂(4,4-bipy)(H₂O)]·4H₂O}_n (HPAc=phenyl acetic acid, 4,4′-bipy=4,4′-bipyridine) was synthesized and characterized by element analysis, IR, TG and X-ray single diffraction crystal structure determination. It crystallizes in the monoclinic space group C2/c with a=2.088 5(4) nm, b=0.839 05(17) nm, c=1.683 5(3) nm, β=105.45(3)° and V=2.843 5(10) nm³, Z=4, M_r=628.94, F(000)=1 288, μ=0.820 mm^-1, R=0.019 9, wR=0.056 5. Each cadmium(Ⅱ) atom is seven-coordinated by four oxygen atoms from two different phenyl acetate groups and two nitrogen atoms from two 4,4′-pyridine ligands and one water molecule, forming a distorted pentagonal bipyramid coordination geometry. Adjacent cadmium(Ⅱ) atoms are bridged by 4,4′-pyridine ligand, constructing a infinite chain along the diagonal direction of ac plane. The Cd…Cd separation within the polymer is 1.164 6(4) nm. The three-dimensional supramolecular structures of the title complexes are constructed by hydrogen bonding interactions and π-π stacking interactions between the benzene rings of HPAc and 4,4′-bipy. CCDC: 616697.     

Two New Low Dimensional Lead(Ⅱ) Diiodide Complexes by Introducing Carbonyls on 1,10-Phenanthroline: a Combined Experimental and Theoretical Study

Two new low dimensional lead(Ⅱ) diiodide complexes with 1,10-phenanthroline-5,6-dione(Phendione), PbI2(Phendione)2(1) and PbI2(Phendione)(DMSO)2(2), have been synthesized by solution processes and structurally determined by X-ray diffraction method. Both compounds are mononuclear with the lead centers being in highly distorted octahedral environments. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Theoretical calculations based on the DFT/B3 LYP level indicate that the introduction of electronic donating groups on the phenanthroline ring can improve the electron density of nitrogen atoms, and they can replace part of the bridged iodine atoms to lower the structural dimensions. Experimental band gaps of about 2.07 and 1.97 eV indicate their semiconductor nature.     

有机体系中电合成纳米PbTiO3粉体及表征

The precursor PbTi(OCH₂CH₃)_6-y(acac)_y for the mixed oxide PbTiO₃was synthesized by electrochemical dissolution of Lead and Titanium with a 1∶2 electricity quality in ethanol and acetyl-acetone solution. Nano-sized PbTiO₃powder was prepared by drying and calcining the xerogel from a direct sol-gel hydrolyzation of the precursor solution under pH of 8.5. The FTIR, TG-DTA, XRD and TEM were employed to characterize the structure of the precursor and nano-sized PbTiO₃. The results showed that the optimized conditions for the preparation of nano-sized PbTiO₃ were the electrolysis of the Lead plate and Titanium plate at 50 ℃ and 40 ℃ respectively under 0.03mol·dm^-3Bu₄NBr solution. The nano-sized PbTiO₃prepared by electrolysis exhibited a dispersive structure with an average diameter of 10 to 15 nm.     

新型一维Cd(Ⅱ)配位聚合物的合成、晶体结构和光致发光性质

A new 1D chain coordination polymer [Cd(dpq)(ox)_0.5Cl]_n(1) (dpq=dipyrido[3,2-d:2′,3′-f]quinoxaline and ox=oxalate) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. Compound 1 (CdClC₁₅H₈N₄O₂): monoclinic, space group P2₁/c, a=0.854 04(5) nm, b=2.094 90(13) nm, c=0.839 22(5) nm, Z=4, V=1.438(15) nm³, M_r=424.11, D_c=1.959 g·cm^-3, F(000)=828.0, μ=1.719 mm^-1, S=1.028, the final R=0.025 8 and wR=0.057 5. The crystal structure analysis indicates that the cadmium ion is coordinated by two oxygen atoms from a oxalate, two chelating nitrogen atoms from a dpq molecule and two Cl^- anions. The adjacent Cd(Ⅱ) ions are linked by Cl^- anions and oxalate ligands in alternate sequence to form a 1D chain coordination polymer and the adjacent chains are further connected by π-π stacking interactions to form a 2D supramolecular network. Moreover, the title compound exhibits blue emission in the solid state at room temperature. CCDC: 680748.     

二维层状镉配合物[Cd(mbix)(BIPA)]的水热合成、晶体结构及荧光性质

A 2D coordination polymer of [Cd(mbix)(BIPA)] (1) (H₂BIPA=5-bromoisophthalic acid and mbix=1,3-bis(imidazol-1-ylmethyl) benzene) has been hydrothermal prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction structure analysis. The crystal is of monoclinic, space group P2₁/n with a=1.002 0(4) nm, b=1.754 4(7) nm, c=1.208 8(5) nm, β=94.271(5), V=2.119 1(15) nm³, D_c=1.861 g·cm^-3, Z=4, F(000)=1 168, Goof=1.085, R₁=0.045 0, wR₂=0.093 1. The crystal structure shows that the Cd₂ units are formed by the two caroboxylate group adopting tridentate-chelating-bridging coordination mode, which are linked to form a 2D layer structure by the ligands, and further extended into a 3D supramolecular structure through C-H…O hydrogen bonding interactions and π-π weak interactions. In addition, complex 1 exhibits strong photolumine-scent emission at room temperature. CCDC: 710801.     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

N，N′-二苄基-苯并咪唑四氯合铜(Ⅱ)化合物的合成、结构和性能研究(英)

A novel N，N′-dibenzyl-benzimidazolium tetrachlorocuprate(Ⅱ) complex, [C₂₁H₁₉N₂]₂[CuCl₄], was synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in monoclinic system, space group P2/c, a=1.203 9(2) nm, b=0.975 0(2) nm, c=1.878 2(6) nm, β=114.12(2)°, V=2.012 2(8) nm³. Its structure was identified by EA, IR and UV spectra and characterized by electrochemistry, thermal and magnetic property. The Cu(Ⅱ) atom of [CuCl₄]^2- has distorted tetrahedral coordination geometry. In the crystal structure, there are strong extensive C-H…Cl hydrogen bonds and π-π stacking interactions, which stabilized the crystal structure. CCDC: 221570.     

锌(Ⅱ)-氨基酸水杨醛席夫碱-α-氨基酸三元配合物的稳定性

The stability constants of binary complexes of Zn(Ⅱ)-α-amino acid and ternary complexes of Zn(Ⅱ)-N-Salicylideneaminio acid (ligand A)-α-amino acid(ligand B) at (25±0.1)℃ and in the presence of 0.1 mol·L^-1 KNO₃ have been determined by pH method. The α-amino acid(Aa) used were Glycine(Gly), L-Serine(Ser), L-Leucine(Leu), L-Proline(Pro) and L-Phenylalanine(Phe). It was found that the linear free energy relationship (LFER) exists nicely between the following parameter pairs logβ₁₀₂ and pK^B₂, logβ₁₁₁ and pK^B₂, and logβ₁₁₁ and pK^A₂. The ΔlgK was used to characterize the stability of ternary complexes related to the stability of parent binary complexes. The hydrophobic interaction between ligands in the ternary complexes was studied.     

牛磺酸缩3，5-二溴水杨醛席夫碱镁配合物[Mg(Br2TSSB)(Phen)(H2O)]·H2O的合成及晶体结构

Reactions of bitter salt with taurine-3,5-dibromo-salicylaldehyde schiff base gave one new Complex [Mg(Br₂TSSB)(Phen)(H₂O)]·H₂O (Br₂TSSB=Taurine 3,5-dibromo-Salicylaldehyde Schiff Base, phen=o-phenanthroline), which was characterized by elemental analysis, IR and X-ray diffraction. The chemical formula weight of the complex is 625.58. It′s crystal belongs to monoclinic system with space group P2₁/c. The cell parameters are: a=1.814 2(3) nm, b=0.814 75(14) nm, c=1.641 7(3) nm, β=90.571(4)°, and Z=4, V=2.426 4(7) nm³, Dc=1.712 g·cm^-3, F(000)=1 248, μ=3.496 mm^-1. The complexes form a 3D net structure in which they are connected with hydrogen bonds and π-π stacking. The Mg(II) formed a distorted coordination tetragonal pyramid. CCDC: 286194.     

一种新的有机-无机混配配位聚合物[Zn(N3)2(bpp)]n的自组装及晶体结构(bpp=1，3-二吡啶丙烷)

A novel coordination polymer [Zn(N₃)₂(bpp)]_n[bpp=1，3-bis(4-pyridyl)-propane] was synthesized at room temperature and structurally characterized by means of X-ray single crystal diffraction. The results show that the polymer exhibits a linear chain structure; the Zn-Zn distance is 12.235?. Each Zn(Ⅱ) ion is coordinated by two nitrogen atoms from bpp ligands and two nitrogen atoms from azido (N₃^-) groups， the coordination geometry of Zn(Ⅱ) ion is a slightly distorted tetrahedron， the angles around Zn(Ⅱ) ions are from 103.27° to 121.37°. In the solid-state structure of the polymer， the linear chains are stacked with parallel mode along a direction. Moreover， between adjacent chains， there are π-π interactions between pyridine rings， which are arranged in face-to-face fashion with interplanar distances of av. 3.821?. CCDC： 189591.     

[Mn(H2O)(phen)2(PAc)](ClO4)的合成、红外光谱及晶体结构

The complex [Mn(H₂O)(phen)₂(PAc)](ClO₄) was synthesized and investigated by elemental analysis, molar conductivity, IR spectrum and X-ray diffraction methods, where phen=1,10-phenanthroline and PAc=phenylac-etate group. The complex crystallizes in the triclinic space group,P1 , with a=0.9289(2)nm,b=1.2425(2)nm,c=1.4791(3)nm,α=114.34(3)°,β=91.25(3)°,γ=104.65(1)°,V=1.4893(4)nm³,Z=2,F(000)=686,D_c=1.489g·cm^-3,μ=0.589mm^-1. The Mn(Ⅱ) ion has a six-coordinate distorted-octahedral geometry with the four nitrogen atoms of two phen ligands,a coordinated-water oxygen atom, and a carboxylate oxygen atom of PAc^-. There is π-π stacking interaction between two phen rings from two neighbor molecules.     

沉淀法合成纳米晶长余辉材料Y2O2S∶Eu3+，Ti

The long-lasting phosphorescent materials, yttrium oxysulfides doped by Eu and Ti, were systhesized by coprecipitation with their subsequent thermal decomposition in the presence of sulphur. The products were characterized by XRD, TEM, phosphorescent spectra, and thermoluminescence. The XRD results indicate that the lowest synthesis temperature is 700 ℃. From the TEM, the average diameter of particles was in the range of 60～120 nm, and augmented with the increase of temperature. The materials under UV excitation presented well afterglow from the transition of ⁵D_0,1 → ⁷F_J of Eu³⁺, and the persistent time was about 2 h. The long-lasting afterglow mechanism was discussed, too.     

水溶液中新型四氮杂二乙酸基取代大环及其镧系配合物的热力学研究

The protonation constants of the macrocycle H₂L¹ (c-meso-2,4,4,11,13,13-hexamethyl-1,5,10,14-tetraazacyclooctadecane-N,N＂-diacetic acids)were determined potentiometricly and by computer fitting in 0.5 mol·L^-1 KNO₃ solution at 25±0.1℃, 30±0.1℃ and 40±0.1℃. The stability constants of the 1∶1 complexes of H₂L¹ with La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺, Yb³⁺ were determined by the same method at 40±0.1℃. The ΔH、 ΔS and ΔG of the coodination reaction of H₂L¹ with H⁺ in the aqueous solution were found.     

铜取代Dawson结构杂多钨磷酸电荷转移配合物的合成与性质研究

Two new charge-transfer complexes, (DMAH)₁₀［CuP₂W₁₇O₆₂］·DMF·2H₂O and (DMAH)₁₄［Cu₂P₂W₁₆O₆₂］ have been prepared in aqueous solution from N,N′-dimethylaniline(DMA) and copper substituted polyoxotungstates with Dawson Structure, and characterized by elemental analysis, ICP, TG, IR, diffusion reflectance electronic spectra, polarography, and CV. The results indicate that the structure of anion has little change after the charge-transfer complexes are formed, but the characteristic vibrational bands have some red shift or blue shift. The charge transfer takes place under sunlight. There is a new absorption band at 625 nm in the solid reflectance electronic spectra of the complexes, it is ascribed to the IVCT (W(V)→W(Ⅵ) band of the reduced anion ［CuP₂W₁₇O₆₂］^10-. The conductivities at room temperature of title complexes are 3.6×10^-9 S·cm^-1 and 5.4×10^-9 S·cm^-1, respectively. Both of them are weak semiconductors.     

Syntheses,Crystal Structures and Intermolecular Interactions of Cu（II） Complexes with Methyl- benzoic Acid （MBA） and 1,10-Phenanthroline

Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.     

Synthesis, crystal structure and luminescence properties of europium complexes with a new terpyridine-like ligand

New 1:1, 1:2 and 1:3 europium (Ⅲ) complexes with 2,4,6-tris(3,5-dimethylpyrazol-1-yl)-1, 3,5-triazine have been prepared, and their luminescence has been demonstrated to be sensitive to the π-π stacking and H-bonding interactions.