Synthesis,Crystal Structures and Magnetic Properties of Cobalt（II） and Manganese（II） Coordination Polymers Constructed from 5-（Pyridin-4-yl）isophthalate Ligands

Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

Synthesis and Crystal Structure of 3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)- pyrrol-2-yl)pentane·2CH_3OH

3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)pyrrol-2-yl)pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·(CH3OH)2, belongs to the orthorhombic system, space group Pccn with a = 18.094(2), b = 11.6890(16), c = 13.3629(19) , V = 2826.3(7) 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F(000) = 1080 and μ(MoKα) = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ(I), and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.     

Two New Cu(Ⅱ) Coordination Polymers Based on 2,5-Furandicarboxylic Acid and 2,2'-bipyridine:Synthesis and Crystal Structure

Two new Cu(Ⅱ) coordination polymers,[Cu(FDA)(BPY)(H2O)]n(1) and {[Cu(FDA)(BPY)(H2O)]·2H2O}n(2)(H2FDA = 2,5-furandicarboxylic acid,BPY = 2,2-bipyridine),have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR.Compound 1 crystallizes in monoclinic,space group P21/c,with a = 7.5915(15),b = 8.4050(17),c = 24.204(6) ,β = 99.05(3)°,V = 1525.1(6) 3,Dc = 1.706 g/cm3,C16H12CuN2O6,Mr = 391.82,F(000) = 796,μ(MoKα) = 1.470 mm–1,Z = 4,R = 0.0633 and wR = 0.1059 for 2389 observed reflections(I 2σ(I)),R = 0.0738,and wR = 0.1098 for all data.Complex 2 belongs to triclinic space group P1 with a = 8.8660(18),b = 8.9112(18),c = 12.525(3) ,α = 88.41(3),β = 69.38(3),γ = 66.95(3)°,V = 845.2(3) 3,Dc = 1.681 g/cm3,C16H16CuN2O8,Mr = 427.85,F(000) = 438,μ(MoKα) = 1.342 mm–1,Z = 2,R = 0.0290 and wR = 0.0690 for 2767 observed reflections(I 2σ(I)),R = 0.0329 and wR = 0.0706 for all data.Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands,which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.     

Synthesis, Crystal Structure and Luminescent Properties of a Novel 2D Sheet Cd(Ⅱ) Coordination Polymer [Cd(Cpna)(Py)]n

A coordination polymer, [Cd(cpna)(py)]n(H2cpna = 5-(2-carboxylphenyl) nicotic acid, py = pyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectra and single-crystal X-ray diffraction. Colorless crystals crystallize in the monoclinic system, space group P21/c with a = 8.589(2), b = 13.047(3), c = 14.940(4) , β = 96.001(2)°, V = 1664.9(7) 3 , C18H12CdN2O4 , Mr = 432.70, Dc = 1.726 g/cm 3 , F(000) = 856, Z = 4, μ(MoKα) = 1.337 mm -1 , the final R = 0.0396 and wR = 0.0891 for 2422 observed reflections (I > 2σ(I)). Complex 1 exhibits a two-dimensional (2D) sheet structure, which further builds a three-dimensional (3D) supramolecular architecture via C-H···O hydrogen-bonding interactions.     

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound Constructed by N-(4,6-Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper(Ⅱ ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dime- thoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) , β = 108.077(2)o, V = 3104.3(5)3, Dc = 1.627 g/cm3, Z = 4, C20H28CuN10O14S2, Mr = 760.18, μ(MoKα) = 0.920 mm–1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I > 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N–H…O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(II) ion, intermolecular C–H…O hydrogen bonds and weak π…π stacking interactions, leading to the formation of a multi-dimen- sional supramolecular network.     

Syntheses,Crystal Structures and Thermal Stability of Two Complexes of La（Ⅲ）/Ce（Ⅲ） Assembled by H2TBTA and Phen

Two 2D layer complexes {[La(TBTA)1.5(phen)2H2O]·3H2O}n (1) and {[Ce(TBTA)1.5(phen)2H2O]·3H2O}n (2) (H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, phen = 1.10-phenanthroline) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. Both crystals belong to monoclinic, space group P21/n. Crystal data for 1: a = 8.7097(11), b = 34.276(4), c = 13.7281(17) , β = 95.397(2)o, V = 4080.1(9) 3, Z = 4, LaC36H24Br6N4O10, Mr = 1290.96, Dc = 2.102 g/cm3, μ(MoKα) = 6.983 mm-1, F(000) = 2460.0, T = 296(2) K, the final R (I > 2σ(I)) = 0.0478 and wR (all data) = 0.0985 for 10127 independent (Rint = 0.0775) and 7137 observed reflections with I > 2σ(I). Crystal data for 2: a = 8.709(2), b = 34.202(9), c = 13.685(4), β = 95.714(4), V = 4055.9(19)3, Z = 4, CeBr6C36H24O10N4, Mr = 1292.17, Dc = 2.116 g/cm3, μ(MoKα) = 7.094 mm-1, F(000) = 2464.0, T = 296(2) K, the final R (I > 2σ(I)) = 0.0590 and wR (all data) = 0.1453 for 10014 independent (Rint = 0.1253) and 6081 observed reflections with I > 2σ(I). Both complexes are allomerism with the general molecular formula of {[M(TBTA)1.5(phen)2H2O]·3H2O}n. In the structures, the H2TBTA ligands adopt a monodentate coordination mode. Both the 2D layer frameworks are further extended to be 3D layers via H-bonding interactions.     

Synthesis and Characterization of a New 2D Ca(Ⅱ) Coordination Polymer Containing 1D Calcium-oxygen Chains

A new 2D Ca(Ⅱ) coordination polymer, [Ca(H2btc)(H2O)2]n(1, H4 btc = biphenyl-3,3',5,5'-tetracarboxylic acid), has been synthesized using the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and photoluminescent analysis. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 17.5676(15), b = 11.4496(8), c = 7.6197(8)A, β = 102.787(2)o, V = 1494.6(2) A3, Z = 4, D3 c = 1.797 Mg·m-, μ = 0.483 mm-1, F(000) = 832, the final R = 0.0348 and wR = 0.0915 for 1521 observed reflections with I 2σ(I). Complex 1 has a 2D network containing 1D calcium-oxygen chains. These 2D networks are further connected by O–H···O hydrogen bonding interactions to generate a 3D supramolecular structure.     

Synthesis,Crystal Structure and DNA-Binding Property of a Mn(Ⅱ) Complex Based on 5-(Tri-fluoromethyl)pyridine-2-carboxylic Acid

A new complex Mn(Htpc)_2(H_2O)_2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?~3, Z = 1, D_c = 1.793 g·cm~(-3), μ = 0.855 mm~(-1), Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.     

Syntheses and Crystal Structures of Two One-dimensional Cobalt(Ⅱ) Compounds with the Flexible Dipyridyl Ligan

Two one-dimensional cobalt(Ⅱ) compounds {[Co(Hbpma)(H2O)4 ] 2 ·3SO 4 ·4.5H2O} n1 and {[Co(Hbpma)(NCS) 3 (H2O)]·2.85H2O}n2 (bpma = N,N -bis(3-pyridylmethyl)amine) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1 with a = 15.8780(5), b = 16.2187(5), c = 16.4858(5) , α = 91.0420(10), β = 94.5190(10), γ = 101.4360(10)°, V = 4145.7(2) 3 , C 24 H 53 Co 2 N 6 O 24.50 S 3 , M r = 1031.76, Z = 4, D c = 1.653 g/cm 3 , μ(MoKα) = 1.046 mm -1 , F(000) = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections (I > 2σ(I)). For complex 2, it belongs to triclinic, space group P1 with a = 9.3761(11), b = 10.5814(13), c = 11.2972(14) , α = 85.472(2), β = 88.058(2), γ = 76.203(2)°, V = 1085.0(2) 3 , C 15 H 21.70 CoN 6 O 3.85 S 3 , M r = 502.79, Z = 2, D c = 1.539 g/cm 3 , μ(MoKα) = 1.112 mm -1 , F(000) = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections (I > 2σ(I)). Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.     

Crystal Structure and Binding Properties of a New Diethoxycarbonyl Glycoluril Derivative:C_(46)H_(34)Cl_4N_4O_8

A new clip molecule 1 based on diethoxycarbonyl glycoluril, C46H34Cl4N4O8, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 11.3674(8), b = 11.3674(8), c = 16.9704(12)A, α = 70.0690(10), β = 72.2310(10), γ = 78.0880(10)°, V = 1993.2(2) A3, Z = 2, Dc = 1.521 g/cm3, μ(MoKα) = 0.361 mm-1, F(000) = 940, the final R = 0.0422 and wR = 0.1144 for 22997 observed reflections with I 2A(I). The crystal structural analysis shows that C–H···O and C–H···Cl hydrogen bonds, C–H···π, C–Cl···π supramolecular interactions, and π-π packing interaction stabilized the whole crystal structure. The binding study by fluorescence spectroscope titration showed that the title molecule can selectively recognize Fe3+ with fluorescence quenching.     

N,N′-双(2-吡啶乙基)二硫代草酰胺根桥联的异三核锰(Ⅱ)铜(Ⅱ)锰(Ⅱ)、镍(Ⅱ)铜(Ⅱ)镍(Ⅱ)和三核镍(Ⅱ)配合物的合成及性质

以取代的二硫代草酰胺根作为桥联配体, 合成了3种新的三核镍配合物[Ni₃(Ped)₂](ClO₄)₂(H₂O) (1)、[Ni₃(Ped)₂](NO₃)₂(H₂O) (2)和[Ni₃(Ped)₂](Ac)₂(H₂O)₂ (3),及2种新的异三核铜镍和铜锰配合物[CuNi₂(Ped)₂](NO₃)₂(H₂O)₂ (4)和[CuMn₂(Ped)₂](NO₃)₂(H₂O)₂ (5) (H₂Ped =N,N′-双(2-吡啶乙基)二硫代草酰胺)。通过元素分析、红外光谱、紫外可见光谱、电导、电子顺磁共振谱等对配合物进行了表征，对配合物进行了热分析。测定了配合物(5)的变温磁化率，研究了配合物(5)中Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用，结果表明在Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用具有高自旋基态的非正规自旋态性质。     

Cu(Ⅱ)-Mn(Ⅱ)-Cu(Ⅱ)异三核配合物的合成与磁性研究

分子磁体化合物的设计合成是近年来迅速发展的一个新兴前沿领域[1,2],它涉及化学、物理、材料等诸多领域,多核配合物体系是分子磁体化合物中研究最为广泛和深入的一类体系.     

Cu(Ⅱ)-VO(Ⅱ),Cu(Ⅱ)-Cr(Ⅲ)和Cu(Ⅱ)-Fe(Ⅲ)异双核配合物的合成及表征

合成了三种二 ( 3 羧基水杨醛叉 )缩丙撑二胺 (TS)的Cu(Ⅱ ) VO(Ⅱ )、Cu(Ⅱ ) Cr(Ⅲ )、Cu(Ⅱ ) Fe(Ⅲ )异双核配合物 ,并用元素分析、摩尔电导、IR光谱、UV光谱室温磁矩对配合物的组成和结构进行了表征。磁性研究表明 ,在Cu(Ⅱ ) Fe(Ⅲ )离子间的磁相互作用是反铁磁性的 ,而Cu(Ⅱ ) VO(Ⅱ )、Cu(Ⅱ ) Cr(Ⅲ )离子间是铁磁性相互作用。     

铅、汞、镉离子的荧光传感器研究进展

化学传感器提供了方便、快捷、廉价的分析检测有毒重金属离子的方法,并具有很高的灵敏度和选择性.它在环境科学、分析化学以及生命科学等领域有广泛的应用前景.本文分别综述了pb²⁺、Hg²⁺、Cd²⁺几种有毒重离子化学传感器的最新研究进展,并展望了该领域的发展趋势.     

Synthesis and properties of one-dimensional Ni(Ⅱ) and Ni(Ⅱ)Cu(Ⅱ) complexes linked by hydrogen bond

Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.     

同一体系中铜(Ⅱ)、铅(Ⅱ)、镉(Ⅱ)、镍(Ⅱ)和钴(Ⅱ)的络合物吸附波及其分析应用

研究了丁二酮肟 氨 氯化铵 柠檬酸钠 明胶 抗坏血酸体系中Cu(Ⅱ )、Pb(Ⅱ )、Cd(Ⅱ )、Ni(Ⅱ )和Co(Ⅱ )的络合物吸附波 ,建立了同时测定水溶液中痕量相应元素的新方法。上述金属络合物分别在 -0 .44、-0 60、-0 .76、-1.0 7和 -1.2 4V左右产生灵敏的极谱波。信噪比为 3时 ,检出限分别为 1.0× 10 - 8、2 .3×10 - 8、1.3× 10 - 8、2 .9× 10 - 1 0 和 3 .6× 10 - 1 1 mol/L。铜、铅、镉、镍和钴的浓度分别为 2 .0× 10 - 8～ 2 .0× 10 - 5,4.8× 10 - 8～ 4.8× 10 - 5,3 .0× 10 - 8～ 3 .0× 10 - 5,5 .4× 10 - 1 0 ～ 5 .4× 10 - 7和 6.8× 10 - 1 1 ～ 6.8× 10 - 8mol/L时 ,与相应峰电流线性关系良好。方法用于同时快速测定实际样品中这些金属离子 ,获得满意结果     

新苯并噻唑偶氮苯甲酸型试剂与钴铁铜钯的显色反应

在苯并噻唑偶氮苯甲酸型试剂分子的苯并噻唑环的5位或(和)6位引入氯原子，或在苯环上与羧基相对或相间的位置上引入不同基团，合成了10个新的苯并噻唑偶氮苯甲酸型试剂。研究了在表面活性剂或有机溶剂存在下，这10个试剂与Co(Ⅱ)、Fe(Ⅱ)、Cu(Ⅱ)和Pd(Ⅱ)的显色反应。讨论了苯并噻唑环上氯原子位置和数目及苯环上不同基团对这些试剂分析性能的影响。一些新试剂与金属配合物的摩尔吸光系数在10^5以上，其中6-Cl-BTAEB的灵敏度高于其它试剂。并研究了试剂结构与性能之间的关系。     

修饰聚合物液-固亲和萃取体系连续分离铜(Ⅱ)、锌(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)

用亚胺基二乙酸（IDA）修饰了聚乙二醇PEG8000，并构建了修饰聚合物-盐-水液-固亲和萃取体系，用于高选择富集与分离金属离子。控制最佳分离条件，成相聚合物吐温80浓度；5%～10%；PEG-（IDA）2含量0.1%；（NH4）2SO4浓度；1.14～1.67mol/L；溶液酸度pH3.20～7.00。连续萃取分离了Cu(Ⅱ）、Zn(Ⅱ）、Co（Ⅱ）及Cu（Ⅱ）、Zn（Ⅱ）、Ni（Ⅱ），并探讨了该萃取体系的萃取机理。从水样、发样等多种样品中，成功地富集并测定了痕量Cu(Ⅱ)和Zn（Ⅱ），结果满意。     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).