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 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.

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.

Studies on the Interaction of Cobalt Mixed-Ligand Coordination Compound Containing Tetrapyrido [3,2-a:2′,3′-c:3″, 2″-h:2■,3■-j] phenazine with DNA

A new monometallic complex [Co(phen)_2tpphz]^(3+) (where tpphz is tetrapyrido [3,2-a:2′,3′-c:3″,2″-h:2′″,3′″-j] phenazine) was synthesized by the reaction of 5, 6-diamino-1,10-phenanthroline with [Co(phen)_2(phendione)]^(3+). It was characterized by elemental analysis, molar conductivity, IR, ~1H NMR, ultraviolet and fluorescence spectroscopy. The interaction of the complex with DNA was also investigated. The complex shows the absorption hypochromicity, fluorescence enhancement, the specific viscosity increased when bound to calf thymus DNA. The cyclic voltammetry (CV) measurement showed a change in peak current with the addition of DNA. All the results provide the support for the intercalative binding mode of the mononuclear complex.

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.

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.

富勒烯-C_(60)衍生物与2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以 2 ,3 二 (溴甲基 )喹喔啉和N 溴代丁二酰亚胺 (NBS)为原料 ,以偶氮二异丁腈 (AIBN)为催化剂 ,在氮气中反应制得 2 溴甲基 3 (二溴甲基 )喹喔啉 (A) ,收率为 2 0 %。以此为中间体与富勒烯C60 反应 ,以 18 冠 6为催化剂 ,按n(A)∶n(C60 ) =1 1∶1 0的物质量比在氮气气氛中经Diels-Alder环加成反应合成了C60 并夹二氮杂蒽 (B) ,收率为 10 6 6 %。并对A和B进行了结构表征。

亚硝酸根的2,3-二氨基吩嗪荧光猝灭法测定

2,3-二氨基吩嗪(DAP)在中性环境中具有强荧光.发现其在酸性介质中能与亚硝酸根离子反应,生成产物在中性环境下荧光很弱,据此建立了一种以DAP为探针,荧光猝灭测定水样中亚硝酸根离子的方法.在最佳测定条件下(0.03 mol/L的硫酸,2.0×10^(-3)mol/L十六烷基三甲基溴化铵,反应温度50℃、反应时间50 min,激发和发射波长分别为435 nm和557 nm),体系荧光强度变化与亚硝酸根浓度在0.1 mol/L^2.1×10^(-6)mol/L范围内呈线性关系,检测限为9.8×10^(-8)mol/L.该方法具有操作简便、灵敏度高、长波长下检测及斯托克位移大的优点.

Dppz配体10,13-位由芳香基取代的新型单核钌配合物的合成

目的本论文以1,10-邻菲罗啉(1,10-phenanthroline,phen)为辅助配体,在主配体联吡啶类(3,2-a:2'-3'-c)吩嗪[pyrido-(3,2-a:2',3'-c) phenazine,dppz]的10,13-位分别引入噻吩、苯并噻吩、呋喃及苯并呋喃,设计并合成出对应4种新型单核二-(1,10-邻菲罗啉)-吡啶类(3,2-a:2'-3'-c)吩嗪合钌(Ⅱ)衍生物。方法首先通过Suzuki偶联反应得到4种苯并噻二唑中间体,然后经Co Cl2催化、Na BH4还原得到邻苯二胺类化合物,再经缩合反应得到对应的目标配合物。结果苯并噻二唑中间体及对应的4种目标配合物通过磁共振氢谱、碳谱及高分辨质谱表征,紫外-可见吸收光谱进一步验证了目标配合物结构的正确性。结论本论文通过多步反应合成出以1,10-邻菲罗啉为辅助配体,主配体dppz的10,13-位分别含有噻吩、苯并噻吩、呋喃及苯并呋喃的4种新型单核多吡啶钌配合物。紫外-可见吸收光谱实验表明尽管4种芳香取代基结构有差异,对应苯并噻二唑中间体和钌配合物的吸收光谱相似。

Theophylline as a new and green catalyst for the one-pot synthesis of spiro[benzo[α]pyrano[2,3-c]phenazine]and benzo[α]pyrano[2,3-c]phenazine derivatives under solvent-free conditions

A green,convenient,high yielding and one-pot procedure for the synthesis of novel spiro[benzo[α]pyrano[2,3-c]phenazine]derivatives by domino multi-component condensation reaction between 2-hydroxynaphthalene-l,4-dione,benzene-l,2-diamines,ninhydrine,and malononitrile in the presence of a catalytic amount of 1,3-dimethyl-7H-purine-2,6-dione（theophylline） as an expedient,eco-friendly and reusable solid base catalyst under thermal,microwave irradiation and solvent-free conditions.This procedure has also been applied successfully for the synthesis of benzo[α]pyrano[2,3-c]phenazines.

A Fluorescent Chemosensor for Dihydrogen Phosphate Ion Based on 2-[2-Hydroxy-4-(diethylamino)phenyl]-1Himidazo[4,5-b]phenazine-Fe^(3+)Ensemble

A long wavelength emission fluorescent(612 nm)chemosensor with high selectivity for H_(2)PO_(4)^(−)ions was designed and synthesized according to the excited state intramolecular proton transfer(ESIPT).The sensor can exist in two tautomeric forms(‘keto’and‘enol’)in the presence of Fe^(3+)ion,Fe^(3+)may bind with the‘keto’form of the sensor.Furthermore,the in situ generated GY-Fe^(3+)ensemble could recover the quenched fluorescence upon the addition of H_(2)PO_(4)^(−)anion resulting in an off-on-type sensing with a detection limit of micromolar range in the same medium,and other anions,including F^(−),Cl^(−),Br^(−),I^(−),AcO^(−),HSO^(−)_(4),ClO^(−)_(4)and CN−had nearly no influence on the probing behavior.The test strips based on 2-[2-hydroxy-4-(diethylamino)phenyl]-1H-imidazo[4,5-b]phenazine and Fe^(3+)metal complex(GY-Fe^(3+))were fabricated,which could act as convenient and efficient H_(2)PO_(4)^(−)test kits.

一维链状配合物{[Fe(SO_4)(DPPZ)_2]·H_2O}_n的水热合成及其晶体结构

以FeSO4和二吡啶[3,2-a:2',3'-c]并吩嗪(DPPZ)为原料,采用水热法合成了一维链状配位聚合物{[Fe(SO4)(DPPZ)2].H2O}n,利用元素分析、红外光谱、X射线单晶衍射和热重分析对其结构进行了表征。该配合物属于单斜晶系,P21/m空间群,a=1.3569(3)nm,b=0.6519(13)nm,c=1.7250(3)nm,α=90°,β=111.29(3)°,γ=90°,V=1.4217(5)nm3,Z=2,dc=1.713g/cm3,μ=0.671mm-1,F(000)=750,R1=0.0491,wR2=0.1250。

gacS基因插入失活对绿针假单胞菌G-05的两种胞外次生代谢物合成的影响

一株来自大棚温室甜椒根际的绿针假单胞菌Pseudomonas chlororaphis G-05,可分泌抗生物质吩嗪-1-羧酸,并具有抑制辣椒疫霉的生物防治功效。【目的】为了系统研究该菌株的生物防治功能及抗生物质合成与分泌机制。【方法】首先通过生化法和16S rDNA同源比对法对该菌株进行系统分类的初步鉴定,再根据基因的同源性从G-05基因组DNA中克隆长1.4 kb的gacS基因的部分保守区段,采用抗庆大霉素基因(gentamycin resistance cassette,aacC1)插入失活的策略构建了该基因突变株G-05S。【结果】在King's B(KMB)或PPM培养基中,突变株G-05S合成吩嗪-1-羧酸的能力受到明显抑制。然而,突变株G-05S分泌的吲哚乙酸与野生株相比无显著差异。互补实验表明,gacS基因的表达可以使突变株G-05S的吩嗪-1-羧酸的合成恢复到野生株水平。【结论】由此推测,GacS(Global activator sensor)对不同次生代谢物的调控具有特异性。

Ru(phen)_2 dppx^(2+)光谱探针法研究道诺霉素与脱氧核糖核酸的相互作用

以核酸分子“光开关”Ru(phen)2dppx2+为探针,分别采用紫外-可见吸收光谱法和荧光光谱法研究了抗癌药物道诺霉素(daunomycin,DNM)与小牛胸腺DNA之间的作用方式,结果表明:DNM是以插入的方式与DNA相互作用。Scatchard方程的研究表明,Ru(phen)2dppx2+与小牛胸腺DNA的结合比为1∶4~1∶5;表观结合常数为2.58×107L/mol。DNM加入后,表观结合常数大大降低,这也表明道诺霉素主要是以插入方式与DNA结合。作为研究核酸分子的荧光探针,与溴化乙锭相比,Ru(phen)2dppx2+具有灵敏度高、毒性低、稳定性好、选择性好、使用方便等优点。

一维链状铁(Ⅱ)配位聚合物的合成与晶体结构(英文)

A coordination polymer,namely [Fe(DPPZ)(dipic)]n(1)(DPPZ =dipyrido [3,2-a:2',3'-c]phenazine and H2dipic=pyridine-2,6-dicarboxylic acid),has been obtained by using hydrothermal synthesis method.The crystal structure was determined by X-ray single crystal structure analysis with the following data:Monoclinic,P21/c,a= 0.794 95(16) nm,b=3.601 1(7) nm,c=0.734 32(15) nm,β=106.07(3)°,V=2.020 0(7) nm3,Z=4,Mr=503.25,Dc=1.655 g·cm-3,F(000)=1 024,μ(Mo Kα)=0.795 mm-1,R=0.038 5 and wR=0.081 0.Complex 1 has octahedral coordination geometry and forms 1D zigzag coordination chains that organize into an unusual 3D supramolecular motif through noncovalent bonds,such as π-π stacking interactions and C-H … O hydrogen bonds.The result of TG analysis indicates that the title complex is stable till 290 ℃.

多吡啶-铜(Ⅱ)-L-苯丙氨酸配合物的合成及表征

合成了 2个新的多吡啶 -铜 ( ) -L-苯丙氨酸配合物 :[Cu( L -Phe) ( TATP) ( H2 O) ]Cl O4· 0 .5 H2 O和 [Cu( L-Phe) ( Dppz) ( H2 O) ]Cl O4。用元素分析、摩尔电导、IR,UV以及电子自旋共振光谱等对配合物进行了表征。推测

[Cu(DPPZ)(L-Ser)]^+与DNA的相互作用及其分析应用研究

研究了DNA与铜(Ⅱ)-L丝氨酸-二吡啶并[3,2-a:2′,3-′c]吩嗪配合物[Cu(DPPZ)(L-Ser)]+相互作用的共振光散射光谱和紫外可见吸收光谱,通过研究体系与溴化乙啶相互作用的荧光光谱特征,证明其作用方式为插入作用。在pH 7.2的缓冲溶液中,[Cu(DPPZ)(L-Ser)]+由于插入作用而在DNA表面聚集,使体系的共振光散射强度增强,最大散射峰在400 nm处。在最佳实验条件下,共振光散射增强的强度与浓度在0.42~4.20 ng.mL-1范围的DNA具有良好的线性关系。方法的检出限为0.29 ng.mL-1。该法用于DNA样品的测定,回收率在97.8%~106.0%之间。

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, Crystal Structure and Luminescence of a New Two-dimensional Pb(Ⅱ) Coordination Polymer

A new two-dimensional Pb（Ⅱ） coordination polymer, [Pb2（L）（tpphz）1.5（NO3）2]·H2O（1）, has been obtained by the hydrothermal reaction of tetrapyrido[3,2-a：2′,3′-c：3′′,2′′-h：2′′′,3′′′-j]-phenazine（tpphz） and 2,2′-bipyridyl-3,3′-dicarboxylic acid（H2L）. It crystallizes in monoclinic, space group P21/c with a = 15.344（3）, b = 14.111（3）, c = 21.963（4） ？, β = 106.89（3）o, V = 4550.1（16） ？3, Z = 4, C48H26N13O11Pb2, Mr = 1375.20, Dc = 2.007 g/cm^3, F（000） = 2628, μ（Mo Ka） = 7.471 mm-1, R = 0.0339 and w R = 0.0808. In 1, the two crystallographically independent tpphz ligands adopt the same bis-chelating coordination mode, but they play different roles in the structure of 1. One type of tpphz ligands bridge the Pb（Ⅱ） cations to generate a zigzig chain, where the L anions are located on one side of the chain. Further, adjacent chains are linked by the other type of tpphz ligands into a two-dimensional layer structure. Additionally, the solid state luminescent property of 1 was also studied at room temperature.

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.