Hydrothermal Synthesis and Crystal Structure of a Novel Isophthalate-bridged Copper(II) Polymer with Two-dimensional Network Structure: [Cu_2(phen)(ipt)_2]_(2n)·nH_2O (ipt = isophthalate, phen = 1,10-phenanthroline)

1 INTRODUCTION donor due to the presence of the protonated carboxyl group; (d) it can form short bridges via one car- Coordination polymers are of great interest due to boxylato end or long bridges via the benzene ring[7]. their physical properties and potential applications in We believe that coordination functionality of isoph- functional materials[1~3]. Aromatic polycarboxylic acids thalate can lead to interesting structures. In this com- such as 1,2,4,5-benzenetetracarboxylic acid[4],…     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalatebridged Zinc(Ⅱ) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)2]2n·3nH2O(ipt = Isophthalate, im = Imidazole)

A new metal-organic coordination polymer [Zn(ipt)(im)2]2n(3nH2O 1 has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/n with a = 10.653(3), b = 17.891(6), c = 10.743(4)(A), β = 117.093(5)°, V = 1822.9(10)(A)3, Mr = 413.65, Dc = 1.507 g/cm3, μ(MoKα) = 1.390 mm-1, F(000) = 840, Z = 4, the final R = 0.0444 and wR = 0.1066 for 2434 observed reflections (I > 2σ(I)). Furthermore, compound 1 shows blue photoluminescent property at room temperature.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalate- bridged Zinc(II) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)_2]_(2n)·3nH_2O (ipt = Isophthalate, im = Imidazole)

1 INTRODUCTION The design and synthesis of metal-organic frame- work structure have been studied widely during the past decade not only because of their intriguing architectures but also their unexpected properties for potential practical applications in a wide number of fields, such as asymmetric catalysis, magnetism, pho- toluminescence and so on[1～3]. These novel struc- tures can be rapidly and efficiently synthesized from simple subunits, where the metal ions, bi- or multi- dentate o…     

Crystal Structure and Characterization of a Binuclear Cd(Ⅱ) Quaternary Coordination Complex [Cd_2(phen)_2Q_2(BP)]_n(phen=1,10-Phenanthroline,BP = Biphenyl-4,4'-dicarboxylic acid,Q=8-Hydroxyquinoline Anion)

The structure of a binuclear cadmium(Ⅱ) quaternary complex,[Cd2(phen)2-Q2(BP)]n 1(phen = 1,10-phenanthroline,BP = biphenyl-4,4'-dicarboxylic acid,Q = 8-hydroxy-quinoline-anion),has been determined by X-ray crystallography and characterized by elemental analysis,IR spectrum and thermogravimetric analysis.It crystallizes in the monoclinic system,space group P21/n with a = 13.1906(18),b = 10.9623(15),c = 16.947(2) ,β = 111.3430(10)°,V = 2282.5(5) 3,Z = 4,Mr = 556.85,Dc = 1.620 g/cm3,F(000) = 1116,μ = 0.994 mm-1 and S = 1.056.In the structure,1D chains are connected via biphenyl-4,4'-dicarboxylic acid,8-hydroxy quinoline anion and binuclear cadmium atoms into an infinite 1-D molecular chain architecture.Via aryl ring π-π stacking interactions a supramolecular structure is formed in 1.     

Synthesis and Structure of 1.5Zn(phen)_3·L·3NO_3 Supramolecule(phen=o-Phenanthroline,L=4-Aminoacetophenone Thiosemicarbazone)

A supramolecular framework,1.5Zn(phen)3·L·3NO3(C63H48Zn1.5N16O9S),has been synthesized.The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide.The crystal belongs to the monoclinic system,space group C2/c,with a = 31.005(2),b = 15.114(2),c = 24.887(3) ,β = 94.260(2)o,Z = 8,V = 11630(2) 3,Dc = 1.489 g/cm3,Mr = 1303.29,λ(MoKα) = 0.71069 ,μ = 0.735 mm-1,F(000) = 5368,Rint = 0.0699,R = 0.0505 and wR = 0.0707.Two independent Zn atoms are both coordinated by six N atoms from three phen ligands.π-π and C-H···π interactions among the L ligands and Zn(phen)3 cations,π-π and C-H···π interactions among the Zn(phen)3 cations and N-H···O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.     

Synthesis and X-Ray Crystal Structure of Two Novel Complexes: [M II(phen)3]2V4O12·phen·22H2O(M II=Co, Ni; phen=phenanthroline)

Summary. Two novel compounds, [Co(phen)₃]₂V₄O₁₂·phen·22H₂O (1) and [Ni(phen)₃]₂ V₄O₁₂·phen·22H₂O (2), were prepared from KVO₃–1,10-phenanthroline (phen)–Co(NO₃)₂, resp. NiCl₂–H₂O reaction systems. The compounds 1 and 2 are isomorphous and crystallize in triclinic system, space group P-1. Their crystal structures are formed by two types of layers parallel to 001: a cationic one consisting of [M^II(phen)₃]²⁺ ions and an anionic one containing the cyclic V₄O₁₂ ^4– anions. The solvate phenanthroline and crystal water molecules are located in the cationic and anionic layers, respectively. The IR spectra of 1 and 2 are consistent with the presence of the cyclic V₄O₁₂ ^4– anions in the complexes.Received November 13, 2002; accepted (revised) February 3, 2003 Published online June 2, 2003     

Synthesis and Crystal Structure of a New Cadmium(Ⅱ) Polymer with One-dimensional Chain Structure: [Cd(5-hip)(phen)]n·nH2O (5-hip =5-Hydroxyisophthalate, phen = 1,10-Phenanthroline)

A new metal-organic coordination polymer [Cd(5-hip)(phen)]n.nH2O 1 has beenhydro- ermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-raydiffraction.The crystal of the complex crystallizes in monoclinic, space group P2/n with a =8.8071(17), b =12.386(2), c = 16.981(3)(A),β= 100.182(2)°, V = 1823.2(6)(A）,3, Mr= 490.73, Dc =1.788 g/cm3,μ(MoKa) = 1.240 mm-1, F(000) = 976, Z= 4, the final R = 0.0458 and wR = 0.1373 for 2864 observed reflections (I＞ 2σ(I)).The Cd atoms are coordinated by two N atoms from the phen ligands and four O atoms from 5-hydroxyisophthalate ligands in a highly distorted octahedral geometry.     

Unusually facile syntheses of [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine) and [RuII(phen)3]2+ (phen = 1,10-phenanthroline)

The salts [Ru^II(L–L)₃](CF₃SO₃)₂ (L–L = bpy or phen) have been prepared in high yields via reactions of [Ru^II(DMF)₆](CF₃SO₃)₂ (DMF = N,N-dimethylformamide), generated in situ by reduction of [Ru^III(DMF)₆]-(CF₃SO₃)₃, with an excess of bpy or phen at room temperature in DMF solutions.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Cu(α-Furacrylic acid)2(phen)

The title complex (C26H18CuN2O6, Mr=517.96) has been synthesized by the reaction of α-furanacrylic acid with 1,10-phenanthroline (phen) in the solvent mixture of water and methanol. Crystal data: monoclinic, space group C2/c with a=2.2927(4), b=1.01248(18), c=1.05061(18) nm, β=111.188(3)°, V=2.274(7) nm3, Dc=1.513 g/cm3, Z=4, F(000)=1060,μ=1.007mm-1, R=0.0320 and wR=0.0781. The crystal structural analysis shows that the copper atom is coordinated with four oxygen atoms from two α-furacrylic acids and two nitrogen atoms from 1,10-phenanthroline, giving a distorted octahedral coordination geometry. The result of electrochemical analysis shows that the electron transfer in the electrode reaction is quasi-reversible.     

系列二亚胺Os(Ⅱ)配合物[Os(L)2(CN)2(phen)](L=PH3,DMSO;phen=1,10-邻二氮杂菲)及[Os(PH3)2(phen)Br2]电子结构和光谱性质的理论研究

采用自旋限制和非限制B3LYP/UB3LYP方法分别优化了系列Os(Ⅱ)二亚胺配合物[Os(L)2(CN)2(phen)][phen=1,10-邻二氮杂菲;L=PH3(1),二甲基亚砜(DMSO)(2)]及[Os(PH3)2(phen)Br2](3)的基态和激发态几何构型.通过TD-DFT方法结合PCM溶剂化模型计算了配合物1～3在二氯甲烷溶液中的吸收和发射光谱并指认了相应的跃迁性质.通过理论化学计算,揭示了π酸配体及π碱配体对配合物磷光发射性质的影响及原因.并进一步解释了配合物3易于在Os-Br键处断裂而发生反应的量子化学机理.对配合物在不同溶剂中的磷光发射性质的计算表明,溶剂对配合物的量子产率存在着影响并且配合物具有溶剂化显色效应.     

Single crystal EPR study of the dinuclear Cu(II) complex [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline): influence of weak interdimeric magnetic interactions

We report powder and single crystal EPR measurements of [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline) at 9.7 GHz. This compound consists of centrosymmetric copper(II) ion dimers, weakly ferromagnetically exchange-coupled (J = +3.2 cm(-1)), in which the dimeric units are linked by hydrophobic chemical paths involving the phen molecules. EPR revealed that the triplet spectra are collapsed by interdimeric exchange interactions mediated by that chemical path. Analysis and simulation of the single crystal EPR spectra were performed using Anderson's exchange narrowing model, together with statistical arguments. This approach allowed us to interpret the spectra modulated by the interdimeric interactions in situations of weak, intermediate, and strong exchange. We evaluated an interdimeric exchange constant J' = 0.0070(3) cm(-1), indicating that hydrophobic paths can transmit weak exchange interactions between centers at relatively long distances of the order of ～10 ?.     

Synthesis and Structure Characterization of a Manganese(Ⅱ) Complex With Eight Coordination Geometry: [Mn(O2CMe)2(phen)2]

The title compound [Mn(O2CMe)2(phen)2] (phen = 1,10-phenanthroline) 1 has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group Pbcn, with a = 12.554(4), b = 10.168(3), c = 17.704(5) (A), V = 2259.7(12) (A)3, Z = 4, C28H22MnN4O4, Mr = 533.44, Dc = 1.568 g/cm3, F(000) = 1100, Rint = 0.0242, T = 293(2) K and μ = 0.631 mm-1. The final R = 0.0687 and wR = 0.1960 for 2046 observed reflections with I ＞ 2σ(I). The structure of the complex consists of one Mn(Ⅱ) core coordinated by two bidentate-bound CH3COO- groups and two η2-phen groups forming an eight-coordinate geometrical configuration.     

手性络合物[M(bpy)_2(phen)]~(2+)和[M(phen)_2(bpy)]~(2+)(M=Ru,Os)圆二色谱的理论解析

应用密度泛函理论,在B3LYP/LanL2DZ水平上对C2对称性的混配络合物[M(bpy)2(phen)]2+和[M(phen)2(bpy)]2+(M=Ru、Os;bpy=2,2'-bipyridine;phen=1,10-phenanthroline)在水溶液中的几何构型进行了优化,并用TDDFT/B3LYP方法和相同的基组计算了其激发能、旋转强度和振子强度,绘制了相应的圆二色谱(CD).在分析有关跃迁性质的基础上,对实验圆二色谱的谱带进行了明确的解析和指认,同时讨论了短波区激子裂分的规律性.结果表明:四种络合物在长波区(λ>320nm)的CD吸收带主要是由d-π*跃迁产生的荷移谱带;短波区(λ<320nm)则是配体上平行于长轴的π-π*跃迁产生的激子耦合带,且对于Λ构型表现为正的手性激子裂分.其中,[M(bpy)2(phen)]2+只显示出正负两个激子带,分属于联吡啶和邻菲咯啉配体;而[M(phen)2(bpy)]2+则有三个激子带,其中左侧的两个(一负一正)属于邻菲咯啉配体,右侧的正带则属于联吡啶配体.此外,尽管激子耦合属于远程相互作用,但用TDDFT计算的激子裂分样式仍是正确的.这些结论对于深入理解有...     

Hydrothermal Synthesis and Crystal Structure of a Lead(Ⅱ) Polymer with a Two-dimensional Network Structure:[Pb_2(PDB)_2(phen)]_n·nH_2O

A new metal-organic complex [Pb2(PDB)2(phen)]n·nH2O (H2PDB=pyridine-3,4-dicarboxylic acid,phen=1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction.The compound crystallizes in triclinic,space group P1 with a=7.2472(5),b=10.6966(8),c=16.2376(12),α=98.2960(10),β=91.6430(10),γ=97.4810(10)o,V=1233.53(16)3,C26H16O9N4Pb2,Mr=942.81,Dc=2.538 g/cm3,μ(MoKα)=13.697 mm-1,F(000)=872,Z=2,the final R=0.0247 and wR=0.0654 for 3886 observed reflections (I 2σ(I)).In the crystal structure,the Pb(1) atom is six-coordinated with four carboxylate oxygen atoms from three different PDB ligands and two nitrogen atoms from phen ligand,showing a distorted octahedral geometry;the Pb(2) atom is four-coordinated with four carboxylate oxygen atoms from four different PDB ligands,showing a distorted tetrahedral geometry.It exhibits a three-dimensional supramolecular network structure formed by hydrogen bonds and π-π interactions.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex [Cd(phen)3]·(ClO4)2·(p-MBA)2·(H2O)2

One new cadmium complex [Cd(phen)3]·(ClO4)2·(p-MBA)2·(H2O)2 has been hydro- thermally synthesized by reacting p-methylbenzoic acid (p-MBA), 1,10-phenanthroline (phen) and cadmium perchlorate. It crystallizes in the triclinic system, space group P, with a = 1.2809(3), b = 1.3431(3), c = 1.3734(3) nm, α = 84.259(4), β = 71.603(3), γ = 74.424(3)o, V = 2.1594(8) nm3, Dc = 1.532 g/cm3, Z = 2, F(000) = 1008, μ = 0.697 mm-1, R = 0.0646 and wR = 0.1648. The crystal structure shows that the cadmium ion is coordinated with six nitrogen atoms from three 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The result of electrochemical property analysis shows that the electron transfer in the electrode reaction is irreversible.     

Synthesis and Crystal Structure of Mo(CO)_4(NNP) (NNP=2-(N-Cyclohexyl-N-diphenylphosphinomethyl)aminopyridine)

1 INTRODUCTION The pyridyl-phosphine ligands have been widely used for many years to synthesize hetero- or homo-nuclear metal complexes[1], as electronic differentiation associated with the hard (N) and soft (P) donor atoms dictates their unique reactivities and coordination modes. One of the most common pyridylphosphines studied to date is (2-C5H4N)PPh2 which displays numerous ligating modes ranging from P-coordination and P,N-chelation to the more common P,N-bridging of two metal …     

Synthesis and Crystal Structure of the Binuclear Complex: [Cu2(phen)2(ip)(Hip)2]·4H2O

A binuclear complex [Cu2(phen)2(ip)(Hip)2]·4H2O has been synthesized by the reaction of Cu(CH3COO)2·H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: monoclinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) (A), β = 105.081(2)°,C24H19N2O8Cu, Mr= 526.95, Z = 8, F(000) = 2160, V= 4478.6(10)(A)3, Dc = 1.563 g/cm3, μ = 1.030mm-1, -24≤h≤16, -13 ≤k≤ 13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357)independent reflections and 3290 observed ones (I＞ 2σ(Ⅰ)). Structural analysis shows that coordination geometry of Cu(Ⅱ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.     

配合物Cu(phen)2 (dca)2的合成及晶体结构

合成了配合物Cu(phen)2 (dca)2(phen=C12H8N2为1,10-邻菲啰啉,dca-为二氰基氨基阴离子),用IR对其结构进行了初步表征,并测定了配合物的晶体结构.该晶体属单斜晶系,空间群为P21/c;晶胞参数a=0.8869(2)nm,b=1.4691(2)nm,c=1.9298(2)nm,β=100.90(1)°;V=2.4691(8)nm3,Z=4,F(000)=1132.00,Dc=1.496g/cm3,R=0.051,RW=0.068.中心铜(Ⅱ)离子分别与两个phen中的四个N原子和两个dca-的两个N原子配位,形成六配位的变形八面体结构.     

Synthesis and Structure of a Novel Macrocyclic Complex [Cd_2(phen)_4(phth)_2]·4H_2O

1 INTRODUCTION In recent years, extensively attention has been fo- cused on the design and synthesis of d10 metal- based complexes[1, 2]. A series of d10 metal-organic frame- works have been described not only because of their intriguing structures but also due to their ptential ap- plications in photoluminescent fields[3～7]. Although phthalate ligand was successfully used to design and synthesize a wide variety of metal complexes, those containing Cd(II) complex are less considered[8～…