Hydrothermal Syntheses and Crystal Structures of Cobalt(Ⅱ) Complexes Constructed by Dipyrido[3,2-a:2',3'-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.

Hydrothermal Syntheses and Crystal Structures of Cd(Ⅱ) and Cu(Ⅱ) Complexes Constructed with 1,3,5-Benzenetricarboxylic Acid and Dipyrido[3,2-a:2?,3?-c]phenazine Ligands

Two novel coordination compounds, [Cd2（HBTC）2（DPPZ）2（H2O）3].2H2O （1） and [Cu2（HBTC）2（DPPZ）2（HEO）]n （2） based on 1,3,5-benzenetricarboxylic acid （H3BTC） and dipyrido[3,2-a：2＇,3＇-c]phenazine （DPPZ） ligands, have been constructed under hydrothermal conditions. Two complexes are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Structural analyses show that both complexes 1 and 2 present the three-dimensional supramolecular structures. In addition, two complexes exhibit luminescence property.

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a：2？,3？-c]phenazine and 2,4＇-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd（2,4＇-bpdc）（DPPZ）]2n·n H2O（1） and [Zn（2,4＇-Hbpdc）2（DPPZ）]· H2O（DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, 2,4＇-H2bpdc = 2,4＇-biphenyldicarboxylic acid） have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction（XRD） and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.

Synthesis,Crystal Structure and Magnetic Behavior of a New Manganese(Ⅱ) Coordination Polymer [Mn(DPPZ)(PZDC)(H_2O)] (DPPZ=Dipyrido[3,2-a:2',3'-c]-phenazine and H_2PZDC=Pyrazine-2,3-dicarboxylic Acid)

The title complex, [Mn（DPPZ）（PZDC）（H2O）] 1 （DPPZ = dipyrido[3,2 -a：2＇,3＇- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid）, has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842（5）, b = 7.5741（6）, c = 20.5755（15）A, α = 90.1160（10）, β = 97.0560（10）, γ = 97.3350（10）°, V= 1025.16（13）A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F（000） = 530, μ（MoKa） = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O（1W） is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0（4） at （x＋ 1, y＋1, z） and symmetric PZDC nitrogen atom N（6） at （1-x, 1-y, 1-z）, which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper(Ⅱ) Complex:[Cu_6(DPPZ)_4(btc)_4(H_2O)_8]·5H_2O

A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.

Synthesis, Structure and Photoluminescence of a Tetranuclear Zinc(Ⅱ) Complex: [Zn_4(SO_4)_2(DPPZ)_4(HSal)_2(OH)_2]

A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.

Synthesis,Structure and Photoluminescence of a Binuclear Zinc(Ⅱ) Coordination Polymer Based on 2-Carboxycinnamic Acid and Dipyrido[3,2-a:2′,3′-c]-phenazine

A binuclear zinc（Ⅱ） complex with 2-carboxycinnamic acid （2-ccm） and dipyrido- [3,2-a：2＇,3＇-c]phenazine （DPPZ）, {[Zn2（2-ccm）2（DPPZ）2]·2H2O}n, was synthesized and characterized by elemental analysis, IR, single-crystal X-ray diffraction, thermal gravimetry and fluo- rescent emission. It crystallizes in monoclinic, space group P21/c with a = 13.409（4）, b = 25.530（7）, c = 13.952（4） A, β = 99.554（3）°, V= 4710（2） A3, Z= 4, C56H36N8O10Zn2, Mr= 1111.67, Dc = 1.568 g/cm3, μ（MoKα） = 1.093 mm^-1, F（000） = 2272, R = 0.0422 and wR = 0.0895. In the crystal, the basic unit of 1 is a binuclear Zn2 entity which is linked by 2-ccm ligand to form a 1D double chain along the a axis. The O-H...O hydrogen bonding and π-π interactions lead to a 3D supramolecular motif. In addition, thermal and luminescent properties of complex 1 have also been investigated.

基于金纳米颗粒聚集的高灵敏Ag^+电致化学发光生物传感器

银离子是一种环境污染物,对其进行灵敏的检测非常重要.本文构建了一种基于金纳米颗粒(AuNPs)聚集的高灵敏Ag^+电致化学发光(ECL)生物传感器.探针DNA依靠Au-S键连接到金电极(GE)表面,用6-巯基-1-己醇(6-Hydroxy-1-hexanethiol,6-MCH)封闭未结合位点,合成尺寸均一的Au NPs,将其与Link DNA连接,通过与探针DNA杂交连接到电极表面.在杂交过程中加入一定浓度的Ag^+孵育后,由于C-Ag^+-C结构形成,诱导Au NPs大量聚集,提高电子传输效率.最佳条件下,传感器检测Ag^+浓度线性范围为0.5 nmol/L^10μmol/L和10μmol/L^500μmol/L,最低检出限0.25 nmol/L,显示出较好的特异性和稳定性.

Synthesis, Crystal Structure and Thermal Behavior of a New Lead Dimer: [Pb(L)(adip)]_(2n)

A new coordination compound, [Pb（L）（adip）]2n （L = 11-fluoro-dipyrido[3,2- a：2＇,3＇-c]phenazine and H2adip = adipic acid）, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pi with a = 8.8764（16）, b = 9.8088（17）, c = 12.948（2） A, α = 81.597（3）, β = 80.183（3）, y = 73.918（3）°, V= 1061.5（3） A3, Z = 2, C24H17FNaO4Pb, Mr = 651.61, Dc = 2.039 g/cm^3, F（000） = 624,μ（MoKa） = 7.997 mm^-1, R = 0.0347 and wR = 0.0795. Adjacent Pb（lI） atoms are bridged by two adip ligands to furnish a dimer with a long Pb.＂Pb distance of 9.019 A. The lateral L ligands from neighboring dimers are paired through the strong π-π interactions, yielding a fascinating 2D supramolecular layer.

基于g-CNQDs的荧光共振能量转移法检测银离子

以尿素和柠檬酸钠为原料,采用低温固态法制备了催化相碳氮量子点(g-CNQDs),构建了基于g-CNQDs的荧光共振能量转移体系(FRET)。Ag^(+)通过与胞嘧啶(C)形成C-Ag^(+)-C复合物诱导3’-端修饰荧光素(FAM)的DNA序列(F-DNA)折叠成发夹型结构,导致g-CNQDs与FAM间荧光共振能量转移效率发生改变,实现Ag^(+)的高灵敏检测。优化了反应时间、缓冲液pH、g-CNQDs用量、F-DNA用量对FRET体系的影响。最佳条件下,Ag^(+)浓度在81.97 pmol/L~163.9 nmol/L范围内,g-CNQDs@F-DNA体系FRET效率与Ag^(+)浓度的对数呈良好线性关系,相关系数为0.9996,方法检出限为67.61 pmol/L。方法用于测定环境水样中Ag^(+)浓度,回收率为92.2%~103.5%。

Nickel Complexes Based on Salicylaldehyde-imine Ligands： Synthesis, Characterization and Catalytic Oligomerization of Ethylene

A series of nickel complexes {NOONR}Ni（A： R=Me; B： R=t-Bu; C： R=OMe） based on salicylalde- hyde-imine ligands was synthesized through Schiff base condensation and metal complexation reaction. Upon activation with methylalurninoxane（MAO）, nickel complexes A--C all exhibited good catalytic activity[turnover frequency=5.2×10^5-16.3×10^5 g/（mol Ni-h）] and oligomer selectivity（above 85%, mass fraction） in ethylene oligomerization. In addition, C8--C12 olefins occupied an important proportion in the products of oligomers. Under the conditions of 4.0 MPa, 25℃ and A1/Ni molar ratio of 275, the catalytic selectivity of A/MAO system toward C8-C12 was about 30. 1%（mass fraction）, and the content of C8--C12 a-olefins was consistently above 70%. Furthermore, besides the ligand environment, the catalytic properties of A-C were substantially affected by experimental parameters, such as the reaction pressure, reaction temperature and A1/Ni ratio.

Photoluminescence properties of dinuclear lanthanide complexes in visible and near-infrared region

Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...