A New 2D Layered Barium Coordination Polymer [Ba（3-NPA）]n： Synthesis,Crystal Structure,Thermal Stability and Luminescent Properties

A new two-dimensional(2D) barium(Ⅱ) coordination polymer [Ba(3-NPA)]n(1) has been obtained by the hydro/solvothermal reaction of the corresponding metal salt with 3-nitrophthalic acid(3-NPAH2). Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction analysis. Compound 1 crystallizes in triclinic, space group P1 with a = 4.9611(3), b = 7.2599(4), c = 12.9463(8) , α = 89.0892(2), β = 80.546(2), γ = 73.211(2)°, V = 440.1(5) 3, Z = 2, C8H3BaNO6, Mr = 346.45, Dc = 2.614 g·cm-3, μ = 4.526 mm-1, S = 1.035, F(000) = 324, R = 0.0168 and wR = 0.0471 for 1712 observed reflections with I 2λ(I).(Δρ)max = 0.458,(Δρ)min =-0.565 e·-3 and(Δ/σ)max = 0.001. In compound 1, each 3-NPA2- ligand links six Ba(ΙΙ) ions and each Ba(ΙΙ) ion attaches to six 3-NPA2- ligands to form an inorganic layer structure in the ab-plane. The phenyl groups of 3-NPA2- ligands are grafted on the two sides of the inorganic layer, resulting in a two-dimensional(2D) layered structure. Furthermore, the thermal stability and luminescent properties of compound 1 have also been investigated in detail.     

A New Terbium(Ⅲ) Coordination Compound with 2-Thiophenecarboxylic Ligand:Synthesis and Crystal Structure

A new coordination compound with formula [Tb(2-TC)3(DMF)]n(1, 2-TC = 2-thiophenecarboxylic ligand and DMF = dimethylformamide) was synthesized by solvothermal method. The structure of compound 1 was determined by single-crystal X-ray diffraction analyses, and characterized by elemental analyses, IR and powder X-ray diffraction. Structure analysis reveals compound 1, exhibiting a one-dimensional chain structure, crystallizes in triclinic space group P21/c, with a = 9.2751(19), b = 16.490(3), c = 15.865(5) A, β = 118.98(2)o, V = 2122.7(9) A3, Dc = 1.916 g/cm3, Mr = 612.45(C18H15NO7S3Tb), F(000) = 1196, μ(MoKα) = 3.67 mm–1, Z = 4, R = 0.0616 and wR = 0.0962 for 3865 observed reflections(I 2σ(I)), and R = 0.1092 for all data. Meanwhile, the photoluminescent properties of compound 1 were also investigated in the solid state at room temperature.     

Synthesis, Structure and Luminescent Properties of a New Terbium（Ⅲ） Complex with 5-Bromoisophthalic Acid

The self-assembly of 5-bromoisophthalic acid (H2BIPA) with Tb(NO3)3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2(BIPA)3(CH3CH2OH)]n (1), which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a = 19.2591(17), b = 8.2537(7), c = 18.5663(17), β = 104.4720(10)°, V = 2857.6(4)3, C26H15Br3O13Tb2, Mr = 1092.95, Dc = 2.540 g/cm3, F(000) = 2040, μ = 9.173 mm-1 and Z = 4. The final R = 0.0324 and wR = 0.0767 for 5299 observed reflections (I > 2σ(I)). Complex 1 displays an unusual three-dimensional (4,6)-connected network with (48.66.8)2(44.62)2(42.84) topology, which is different from [Tb(HBDC)(BDC)(H2O)4]·3.3H2O (BDC = isophthalate) because the -Br substituent of isophthalate results in different electronic effect and steric hindrance to change the coordination modes of carboxylate groups in the assembly process. Moreover, luminescent properties of 1 have also been investigated in the solid state.     

Synthesis, Structure and Comparison of Luminescent Property between Two Hexanuclear Silver（I） Thiosemicarbazone Clusters

A new silver(Ⅰ) compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710(9), b = 16.9281(13), c = 17.2984(13), α = 112.8500(10), β = 103.4890(10), γ = 102.6860(10)°, V = 3020.9(4) 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ(MoKα) = 1.108 mm-1, F(000) = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections (I > 2σ(I)). Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver(Ⅰ) cluster. In the cluster, the S atom of ligand L4 (L4 = 2-quinolinecarboxaldehyde thiosemicarbazone) serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Mn2（phen）2（p-CBA）4（H2O）

One novel complex Mn2(phen)2(p-CBA)4(H2O) has been hydrothermally syn- thesized from p-chlorobenzoic acid (p-CBA), 1,10-phenanthroline (phen) and anhydrous man- ganese(Ⅱ) sulfate and then characterized. Crystal data for this complex: monoclinic, space group C2/c, with a = 2.3416(3), b = 1.5604(2), c =1.5605(2) nm, β = 121.048(2)o, V = 4.8849(12) nm3, Dc = 1.510 g/cm3, Mr = 555.26, Z = 8, μ = 0.798 mm-1, F(000) = 2256, GOOF = 1.032, the final R = 0.0393 and wR = 0.0816. The crystal structure shows that two neighboring manganese(Ⅱ ) ions are linked together by two bridge-chelating p-chlorobenzoic groups and one bridging water molecule, forming a cage structure with the Mn–Mn bond distance of 0.3512 nm. Each manganese(Ⅱ ) ion is coordinated by two nitrogen atoms of one 1,10-phenanthroline molecule and four oxygen atoms from three p-chlorobenzoic acid anions and one water molecule, giving a distorted octahedral coordination geometry. The cyclic voltammetric behavior of the complex was also investigated.     

Synthesis,Crystal Structure and Photophysical Properties of Cu（Ⅰ） Complexes Containing 2,5-Bis（pyridyl）-1,3,4-oxadiazole

Four novel Cu(Ⅰ) complexes,[Cu(o-PYO)(PPh3)2]BF4(1),[Cu(o-PYO)(DPEphos)]BF4(2),[Cu2 (o-PYO)(PPh3)3(CH3CN)](BF4)2(3) and [Cu2(o-PYO)(DPEphos)2 ](BF4)2(4) (o-PYO=2,5bis(pyridyl)-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis(2-(diphenylphosphanyl)phenyl)ether),have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer (MLCT) absorption bands in the region of 360-480nm.Four Cu(I) complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.     

Synthesis and Crystal Structure of Bis（barbiturato） triwater Complex of Copper（Ⅱ）

1 INTRODUCTION A variety of transition metal complexes with barbiturates have been prepared owing to their important roles in clinical detection and identi- fication of drug[1～5]. They have the general formula of M(Ⅱ)(barb)2L2, where M is a transition metal (Co, Cr, Zn, Cu etc), barb the anion of a substituted barbituratic acid and L an organic base, usually pyridine. In these complexes, the donor atom in the barbiturate anion is a deprotonated nitrogen atom and, the coordination …     

Synthesis, Structure and Luminescent Properties of Polymeric Copper（Ⅰ） Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper(I) halide complexes bearing phosphine and N-donor bridging ligands,[(PPh3)2Cu2(μ-Br)2(μ-4,4′-bipy)]∞ 1 (bipy=bipyridine),[(PPh3)2Cu2(μ-Br)2(μ-bpe)]∞ 2 (bpe=trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3,were synthe-sized by the multilayer diffusion method,and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic,space group P1 with a=9.122(3),b=9.322(3),c=13.201(4),α=106.440(4),β=105.965(5),γ=94.167(5)°,V=1021.3(6) 3,Mr=967.62,Z=1,Dc=1.573 g/cm3,F(000)=486,μ=3.111 mm-1,the final R=0.0383 and wR=0.0960 for 2792 observed reflections (I > 2σ(I)). Complex 2 crystallizes in triclinic,space group P1 with a=9.420(3),b=10.209(4),c=12.407(4),α=104.136(6),β=108.132(5),γ=95.338(6)°,V=1081.0(7) 3,Mr=496.83,Z=2,Dc=1.526 g/cm3,F(000)=500,μ=2.941 mm-1,the final R= 0.0445 and wR=0.1117 for 3251 observed reflections (I > 2σ(I)). Complex 3 crystallizes in triclinic,space group P1 with a=8.32(1),b=11.53(2),c=13.94(3),α=109.57(3),β=93.85(3),γ= 97.28(3)°,V=1242(4) 3,Mr=1074.59,Z=1,Dc=1.436 g/cm3,F(000)=548,μ=1.279 mm-1,the final R=0.0786 and wR=0.1586 for 2266 observed reflections (I > 2σ(I)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.     

Synthesis,Crystal Structure and Luminescent Properties of a Novel 1D Zigzag Chain Barium(Ⅱ) Coordination Polymer

A new coordination polymer {[Ba(L)(H2O)5]·H2O}n(1, H2 L = 3,3'-((((ethane-1,2-diylbis(oxy))-bis(2,1-phenylene))bis(methylene))bis(oxy))dibenzoic acid) has been synthesized under evaporation process and characterized by elemental analysis, IR spectra, TG analysis,fluorescence spectrum, powder X-ray diffraction analysis and single-crystal X-ray diffraction.Complex 1 crystallizes in the monoclinic system, space group P21/c, with a = 20.918(5), b =7.4539(2), c = 20.168(5) A, β = 95.486(2)o, V = 3130.1(1) A3, Z = 4, C30H34 Ba O14, Mr = 755.91, Dc =1.604 g/cm3, F(000) = 1528, μ = 1.34 mm-1, the final R = 0.0404 and w R = 0.0676 for all data.Single-crystal X-ray structural reveals that the Ba(II) ion adopts a nine-coordinated distorted tricapped trigonal prism coordination geometry. Adjacent Ba(II) ions are linked by one μ2-L2- anion and two(μ2-H2O) water molecules to generate an infinite 1D zigzag chain structure. Then these chains are further linked into a 2D layer supramolecular architecture through O–H···O hydrogen bonds. Luminescent property and thermal stability of complex 1 were investigated.     

Synthesis and Crystal Structure of 4,5-Bis（2-chloroethylthio）phthalonitrile

A novel phthalonitrile compound,[C12H10Cl2N2S2],has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group P21/n with a = 10.6417(8),b = 7.5737(6),c = 18.2758(14),β = 105.2480(10)°,Mr = 317.24,V = 1421.12(19)3,Z = 4,Dc = 1.483 g/cm3,F(000) = 648,μ = 0.733 mm-1,R = 0.0173 and wR = 0.2183.In the structure,the C atoms of the aromatic ring,the two cyanide groups and the two S atoms are almost coplanar(maximum deviation from the mean plane = 0.049(7) ).Two potential weak intermolecular interactions of C-H…N and one type of π…π stacking interaction with a centroid-centroid separation of 3.751(8) stabilize the crystal structure.     

Synthesis,Crystal Structure and Luminescent Property of an Eu~(3+) Complex

A new Eu(Ⅲ) complex, {[Eu(tta)2(C2H5OH)(NO3)]2(bmp)}·bmp(tta = 2-thenoyltrifluoro- acetonate, bmp = 2,2'-bipyrimidine), has been synthesized and characterized by elemental analysis, IR, luminescence and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/n space group, with a = 11.894(6), b = 14.235(8), c = 19.078(10) , β = 103.423(9)o, V = 3142(3) 3, Z = 2, Mr = 1721.10, Dc = 1.819 g/cm3, F(000) = 1696, the final R = 0.0452 and wR = 0.1398 for 5375 observed reflections with I 2σ(I). In the complex, each Eu(Ⅲ) ion is coordinated with four oxygen atoms from two tta ligands and two nitrogen atoms from a bmp ligand, three oxygen atoms from one NO3- anion and one ethanol molecule, forming a distorted tricapped trigonal prism geometry. Luminescence measurement indicates that the europium complex is a strong red emitter in the solid state at room temperature.     

Synthesis,Crystal Structure and Nonlinear Optical Properties of a new cluster compound: MoS4Cu3(PyPPh2)3Cl

Reaction of [NH₄]₂[MoS₄], CuCl and PyPPh₂ in the solid state produces a cube-like cluster. The cluster crystallizes in the orthorhombic space group P2₁2₁2₁ with four formula units in a cell of dimensions a = 12.8980(10) , b = 17.6820(10), c = 22.665(2) Å. Anisotropic refinement for all nonhydrogen atoms yielded the values R = 0.0397 and R _w = 0.1185 for 8803 observed reflections. The structure is built up from three [Cu(Ph₂PPy)]⁺ units bridged by MoS^2? ₄ to form a tetranuclear symmetrical cube-like molecule. Investigation of the third-order optical nonlinear value showed that it exhibits a considerable nonlinear absorptive and self-defocusing effect with α₂ = 1.3 × 10^?11 m w^?1 and n ₂ = ? 3.2 × 10^?18 m² w^?1 in a 1.5 × 10^?4 M DMF solution.     

Synthesis, Structure and Properties of Co(NH_2CSNHNH_2)_3Cl_3·1/2HCl

The single crystal of title compound was obtained in the solution of DMF and CH3OH under the radiation of IR lamp. The crystallographic parameters obtained are as follows: trigonal system, space group P 31C, Z=4, a=b=1.0008(2) nm, c=2. 4011 nm; final R=0. 099, Rw = 0. 092. The properties of title compound were characterized by IR, UV, EPR, XPS and CV measurements.     

二维网状Pb(Ⅱ)配合物的合成、晶体结构及荧光性质

利用4-吡啶-3-苯甲酸(4,3-pybz)和醋酸铅在水热条件下合成了一种新型金属配合物[Pb(4,3-pybz)2]_n(1),并对其进行了元素分析、红外光谱、热重表征、X 射线单晶衍射测定。该配合物为正交晶系,Pccn空间群,a=1.070 74(7) nm,b=2.138 03(13) nm, c=0.865 65(5) nm,V=1.981 7(2) nm³,Z=4,D_c=2.023 Mg·m^-3,F(000)=1 152,GOF=1.050,μ=8.549 mm^-1,残差因子R₁=0.013 9,wR₂=0.032 4。该配合物展现了一个具有(4,4)拓扑二维波浪状网络结构,进而通过弱的π-π相互作用拓展为三维超分子体系。此外,室温下配合物1展现了弱的荧光性质。     

吡啶基双苯并咪唑的合成及其荧光性能

以多聚磷酸(PPA)为催化剂和溶剂,氮气保护下,吡啶基芳香二酸与邻苯二胺经缩合反应合成了三个新的吡啶基双苯并咪唑化合物(2a~2c),其结构经¹H NMR, ¹³C NMR, FT-IR和元素分析表征。2a~2c的固体荧光发射波长分别为473 nm, 427 nm和453 nm。     

对三氟甲基苯甲酸和2，2′-联吡啶双核铽配合物的合成、晶体结构及发光性质

A new dinuclear complex [Tb₂(BA)₆(2,2′-bipy)₂] (BA=4-(trifluoromethyl)benzoic acid, 2,2′-bipy=2,2′-bipyridine) has been synthesized. The complex was characterized by X-ray single-crystal structure analysis. The complex is a dimer with an inversion center. In the complex, two Tb3+ ions are linked by four carboxylate groups of BA ligands in bridging-bidentate coordination mode. Each Tb³⁺ ion is eight-coordinated with two nitrogen atoms from one 2,2′-bipy molecule, four oxygen atoms from four bridging-bidentate BA ligands and two oxygen atoms from one chelating-bidentate BA ligand. Intermolecular hydrogen bonds are formed in the crystal. The complex exhibits strong green fluorescence under ultraviolet light and the fluorescence spectrum consists of four lines peaking at 489, 545, 584 and 620 nm, which are corresponding to the ⁵D₄→⁷F_j (j=6～3) transitions of Tb³⁺ ion, respectively. CCDC: 727763.     

Synthesis,Crystal Structure and Luminescent Properties of a Novel Zinc(II) Complex of N-Acetyl-L-glutamic Acid and Imidazole Ligands

1 INTRODUCTION As is well known, some transition metal ions play an important role in controlling the behavior of many biological macromolecules and produce pro- found effects on their biological actions, medicine and people’s health[1～3]. Zinc is an essential com- ponent of many proteins. In the active sites of zinc enzymes, zinc is bound to the nitrogen of imidazole groups and oxygen of carboxylate groups of amino acids[4～6]. Additional interest in these proteins lies in the fact th…     

含钒氧链阴离子的苯基三联吡啶钴配合物的合成、晶体结构及性质研究

利用水热反应合成一种新型含钒氧链阴离子的苯基三联吡啶钴配合物{[Co(PhTPY)2]V3O9.3H2O}n(PhTPY=4′-ph-2,2′∶6′,2″-terpyridine)。用元素分析、红外光谱和X-射线单晶衍射对其结构进行了表征,该配合物晶体属单斜晶系,C2/c空间群。同时测定了配合物的热稳定性、荧光性质和磁性质。     

含能配合物[Mn(DAT)6](ClO4)2的合成、晶体结构、热行为及感度性质

合成了新型含能配合物[Mn(DAT)6](ClO4)2(DAT=1,5-二氨基四唑), 用X射线单晶衍射法测定了其晶体结构. 该晶体属三方晶系, P3c1空间群, a=b=1.18435(17) nm, c=1.3081(3) nm, α=β=90°, γ=120°, V=1.5891(5) nm3, Z=2. 该配合物分子结构单元中有1个Mn2+离子、6个DAT分子和2个ClO4-离子. 由6个DAT分子中的6个N原子与中心Mn2+离子配位形成六配位、非中心对称的畸变八面体结构. 利用元素分析、差示扫描量热分析(DSC)、热重-微分热重分析(TG-DTG)等方法进行了表征, 研究了其感度性能. 研究结果表明, 该配合物对外界刺激具有很高的响应性和危险性.