1,10-邻菲啰啉并咪唑衍生物阴离子受体的合成及识别性能

设计合成了2个1,10-邻菲啰啉并咪唑衍生物阴离子受体2-(2-羟基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(1)和2-(2-羟基-5-溴苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(2), 受体2的结构由X射线单晶衍射分析确证. 通过紫外-可见光谱滴定及 ¹H NMR滴定研究了这2个受体对F^-, Cl^-, Br^-, I^-, H₂PO₄^-和AcO^- 6种阴离子的识别传感作用及作用机理. 结果表明, 受体对AcO^-, F^-和H₂PO₄^-有较强的传感作用, 溶液颜色由淡黄色变为黄色; 对Cl^-的作用较弱; 而对Br^-和I^-则无明显作用. 通过机理研究发现, 受体与F^-, H₂PO₄^-和AcO^-形成1: 1的氢键超分子, 当阴离子的量超过受体的1倍以后, 咪唑氮上的氢转移到阴离子; 受体与Cl^-以氢键形成超分子复合物, 而与Br^-和I^-作用很弱.     

Synthesis and Crystal Structure of a New Lead Coordination Polymer： [Pb（L）（1,4-ndc）]

The title coordination polymer, [Pb(L)(1,4-ndc)] 1 (L = 2-(4-fluorophenyl)-1Himidazo[4,5f1,10]phenanthroline, 1,4-ndc = naphthalene-1,4-dicarboxylic acid), has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR and singlecrystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 10.1043(11), b = 14.3162(15), c = 17.6061(18), β = 95.3990(10)°, V = 2535.5(5)3, Z = 4, C31H17FN4O4Pb, Mr = 735.68, Dc = 1.927 g/cm3, F(000) = 1416, μ(MoKa) = 6.709 mm-1, R = 0.0201 and wR = 0.0489. The 1,4-ndc dianions link neighboring Pb(II) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the c axis. The C–H···π interactions between the carbon atom of L ligand and the benzene ring of 1,4-ndc lead the one-dimensional chains to form a two-dimensional supramolecular layer. The π-π interactions between L ligand and 1,4-ndc ligand make the two-dimensional layers generate a three-dimensional supramolecular architecture. Additionally, the N–H···O hydrogen bonds further stabilize the structure of 1.     

A New Cadmium(Ⅱ) Dimer Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Syntheses,Crystal Structure and Photoluminescence

In this work, a new Cd(II) dimeric compound, [Cd(Cl)2(L)(H2O)]2(1, L = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 8.944(2), b = 18.781(5), c = 10.904(3), β = 91.392(4)°, V = 1831.2(8) 3, Z = 2, C38H26Cd2F2Cl4Cl4N8O2, Mr = 1031.27, Dc = 1.870 g/cm3, F(000) = 1016, μ(Mo Ka) = 1.513 mm-1, R = 0.0532 and w R = 0.1407. Each Cd(II) atom is in an octahedral coordination sphere, completed by two nitrogen atoms from one L ligand, two chlorine anions, and one water oxygen atom. Two chlorine anions bridge two Cd(II) atoms to give a dimer [Cd(Cl)2(L)(H2O)]2. Adjacent dimers are stacked by one type of π-π interactions among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interactions among L ligands to give a 2D supramolecular layer. Finally, the luminescent property of 1 has been studied in solid state at room temperature.     

Synthesis and Crystal Structure of a New Zn(Ⅱ) Complex Exhibiting Strong Luminescence

The title complex,[Zn(ip)2(H2O)2][ZnCl4]·H2O·2DMF 1(ip=imidazo[4,5-f][1,10] phenanthroline),has been synthesized via the slow evaporation of concentrated reaction solution at room temperature.It was characterized by single-crystal X-ray diffraction.Crystal data for C32H36Cl4N10O5Zn2:white prism,0.17mm×0.15mm×0.10mm,monoclinic,space group P2/c,a=11.928(8),b=9.868(6),c=16.520(11),β=104.879(12)°,V=1879(2)3,Z=2,Mr=913.25,Dc=1.614 g/cm3,F(000)=932,μ=1.616 mm-1,λ(MoKα)=0.71073,GOOF=1.045,R=0.0710 and wR=0.1755 for 3055 observed reflections with Ⅰ2σ(Ⅰ).X-ray diffraction study reveals that the title complex has an interesting 3D architecture via hydrogen bonding interactions and π-π interactions.The IR,TGA,XRD and luminescent properties of complex 1 were also studied.     

微波辅助合成菲并咪唑衍生物及微波非热效应

以1,10-邻菲啰啉5,6-二酮及苯甲醛(或取代苯甲醛)为原料, 在微波辐射条件下制备了一系列菲并咪唑类衍生物, 考察了温度、 时间以及投料比对微波辅助合成菲并咪唑类衍生物的影响, 并进一步探讨了微波非热效应的影响. 设计正交实验优化了反应条件; 使用SiC管作为反应容器屏蔽微波对反应的影响; 通过元素分析、 核磁共振波谱、 质谱及红外光谱等对化合物进行了表征. 结果表明, 微波辅助反应的最佳反应条件为: 1,10-邻菲啰啉-5,6-二酮与苯甲醛(或取代苯甲醛)的投料比为1: 1.5, 反应温度为100℃, 反应时间为20 min; 并且发现SiC管中反应的产率明显低于石英管反应容器. 与传统制备方法相比, 微波辅助合成方法可在更短时间内快速方便地制得菲并咪唑类衍生物; 反应温度、 反应时间以及投料比对微波辅助合成反应有明显影响; 微波非热效应有助于提高反应产率.     

Synthesis, Structure and Characterization of a New 1D Coordination Polymer:[Pb(L)(cis-1,4-chdc)]·0.5H2O

A new 1D coordination polymer, [Pb(L)(cis-1,4-chdc)]·0.5H2O (cis-1,4-chdc = 1,4-cyclohexanedicarboxylate and L = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been synthesized under hydrothermal conditions and characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.153(5), b = 10.338(5), c = 13.074(5), α = 80.956(5), β = 89.725(5), γ = 80.534(5)°, V = 1204.8(10)3 , Z = 1, C54H44F2N8O9Pb2 , Mr = 1401.35, Dc = 1.931 g/cm3 , F(000) = 678, μ(MoKa) = 7.055 mm-1 , R = 0.0277 and wR = 0.0559. Each cis-1,4-chdc anion coordinates with two Pb(Ⅱ) atoms in a bis-chelating coordination mode. In this way, cis-1,4-chdc anions bridged the neighboring Pb(Ⅱ) atoms to generate a 1D chain structure. The L ligands from neighboring chains are paired through the strong π-π interactions to generate a fascinating 2D supramolecular layer.     

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescent Property of Complex [Zn(L)(SO4)]·0.5H2O

Complex [Zn(L)(SO4)]·0.5H2O (L= 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) has been synthesized under hydrothermal conditions. The compound was characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21 /n with a = 9.9916(7), b = 12.3834(9), c = 29.259(2) , β = 97.7720(10)°, V = 3587.0(4)3 , Z = 2, C76H41Cl4F4N16O9S2Zn2 , Mr = 1734.91, Dc = 1.606 g/cm 3 , F(000) = 1754, μ(MoKa) = 0.959 mm -1 , R = 0.0492 and wR = 0.1385. The asymmetric unit of 1 contains one Zn(II) atom, two L ligands, one sulfate anion and half a water molecule. Each Zn(II) atom is five-coordinated by four nitrogen atoms from two different L ligands and one sulfate oxygen atom in a tetragonal pyramidal coordination environment. The N-H···O hydrogen bonds link the discrete structure of 1 into a 2D supramolecular architecture. The photoluminescent property of 1 has also been studied in the solid state at room temperature.     

一个基于2-(2-羧基苯基)-1H-咪唑并[4,5-f][1,10]邻菲哕啉配体的二维铅(Ⅱ)配合物的水热合成及晶体结构

在水热条件下,利用邻菲哕啉衍生物2-(2-羧基苯基)-1H-咪唑并[4,5-f][1,10]邻菲啰啉(HL)和Pb(NO3)2反应合成了一个配合物[PbL2]n(1),并用红外、元素分析和X射线单晶衍射对其结构进行了表征.配合物1属于单斜晶系,空间群为P21/c,晶胞参数a=1.345 9(9) nm,b=0.709 4(5) nm,c=3.265 5(2) nm,β=99.6260(10)°,V=3.074 0(4) nm3,Z=4,C40H22N804Pb,Mr=885.85,Dc=1.914 g·cm-3,μ(Mo Kα)=5.551 mm-1,F(000)=1 728,GOOF=1.038,R=0.027 0,wR=0.058 1,其中5 067个可观测点(I＞2σ(I)).结构分析表明配合物1为二维层状结构.此外,对配合物的热稳定性和发光性质也进行了研究.     

一维链状锌配位聚合物[Zn(Pyphen)(PZDC)(H2O)]的水热合成、结构与荧光性质

The title coordination polymer, [Zn(Pyphen)(PZDC)(H2O)] (1) (Pyphen=pyrazino [2,3-f][1,10]phen-anthroline and H2PZDC=pyrazine-2,3-dicarboxylic acid) has been obtained by using hydrothermal synthesis andcharacterized by elemental analysis, IR, TG, fluorescence spectrum and X-ray diffraction single-crystal structureanalysis. The crystal is of triclinic, space group P1 with a=0.681 8(14) nm, b=0.743 9(15) nm, c=1.759 8(35) nm,α=94.329(30)°,β=95.514(30)°,γ=97.043(3)°,V=0.878 2(3)nm3,Z=2,Mr=481.73,Dc=1.822 g·cm-2,μ=1.452 mm-1,F(000)=448, Rint=0.033 9, R=0.042 5, wR=0.090 7. In complex 1, PZDC ligands link the Zn(Ⅱ) ions to form 1Dchain structures, and further extended into a 3D supramolecular framework through π-π interactions andhydrogen bonding interactions. In addition, complex 1 exhibits strong photoluminescence at room temperature.     

由MOPIP配体构筑的两种金属配合物的合成、表征及晶体结构(英文)

采用水热法由2种不同金属盐和MOPIP(MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)配体合成了2种新型零维配合物[Cd(MOPIP)3(H2O)9]4n(1)和[Mn(MOPIP)3(H2O)6]2n(2),并对其进行了元素分析、红外光谱表征、热失重和X射线单晶衍射测定。结果表明,每个金属中心离子与来自3个不同MOPIP分子上的6个氮原子进行配位,形成畸变的八面体构型。     

Off-on-off luminescent switching of a dye containing imidazo[4,5-f][1,10]phenanthroline

A new acid-base fluorescent switch containing both imidazo[4,5-f][1,10]-phenanthroline and triphenylamine groups has been synthesized.Its fluorescence emissions and absorptions can be reversibiy changed through protonation/deprotonation of imidazole and amine moiety by controlling the intramolecular charge transfer(ICT) process,leading to off-on-off fluorescent molecular switching.     

以对苯二甲酸及咪唑并[4,5-f][1,10]邻菲咯啉为配体的镉(Ⅱ)、锌(Ⅱ)配合物的构筑及晶体结构

在水热条件下,以对苯二甲酸(H2bdc)和咪唑并[4,5-f][1,10]邻菲咯啉(Imphen)为配体构筑了两种配合物[Cd(bdc)(Imphen)(H2O)]n·nH2O(1)和[Zn(bdc)(Imphen)(H2O)]n·nH2O(2),并利用元素分析和X-射线单晶衍射对其结构进行了表征。结构分析表明:bdc2-在2个配合物中展示了不同的配位模式,配合物1和2都具有一维链状结构,并且都通过分子间氢键和π-π相互作用形成三维网状结构。此外,对配合物的热稳定性和发光性质也进行了研究。     

1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

芳基咪唑并[4,5-f][1,10]菲咯啉的无溶剂绿色合成研究

以菲咯啉二酮、苯甲醛及其衍生物和醋酸铵为原料,采用无溶剂绿色研磨工艺,合成了芳基咪唑并菲咯啉化合物.通过对不同反应条件的筛选,得到一条高效、简便、绿色的合成芳基咪唑并菲咯啉化合物路线,不同的芳醛与菲咯啉二酮都可以较高的收率得到相应的芳基咪唑并[4,5-f][1,10]菲咯啉.     

Diastereoselective Synthesis of 1,10-Dihydropyrrolo [ 1,2-a] [1,10]phenanthroline Derivatives via 1,3-Dipolar Cycloaddition Reaction

The functionalized 1,10-dihydropyrrolo[1,2-a][1,10]phenanthroline derivatives were synthesized in good yields and with high diastereoselectivity by 1,3-dipolar cycloaddition reactions of N-phenacylphenanthrolinium bromides or N-ethoxycarbonylmethylene phenanthrolinium bromide with various nitrostyrenes in acetonitrile at room temperature in the presence of triethvlamine,     

新型2-取代苯基-1H-咪唑[4,5-f][1,10]邻菲啰啉基Ru(II)配合物的光电性质

为获取具有活性官能团的接枝型、高性能荧光传感配合物,合成了2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NH2)、2-(4-羟基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-OH)、2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-COOH)和2-(4-硝基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NO2)四种配体,借助紫外-可见(UV-Vis)吸收光谱、荧光(PL)光谱、循环伏安法(CV)和含时密度泛函理论(TD-DFT)对上述四种配体与过渡金属元素钌(Ru)所形成的配合物的光电性能进行研究.结果表明:四种配合物均在可见光区域有较强吸收,发光范围覆盖绿色到红色光波段.在极性溶剂N,N-二甲基甲酰胺(DMF)中,以2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉为配体所构建的钌配合物([Ru(CImPB-NH2)(bpy)2]2+的荧光量子产率(Φ)较不含咪唑环的5-氨基邻菲啰啉合钌([Ru(phen-NH2)(bpy)2]2+)的提高了67%,以2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉所构建的钌配合物([Ru(CImPB-COOH)(bpy)2]2+)的Φ可达29.8%,是[Ru(phen-NH2)(bpy)2]2+的18倍.理论计算表明:配体中取代苯环、咪唑环和邻菲啰啉的稠环共平面,形成共价大π体系,其有效共轭长度较邻菲啰啉母体有显著增加,配合物是以Ru为中心的近似八面体构型,理论计算的电子吸收光谱和跃迁性质与实验结果相一致.上述研究有可能为接枝型、高性能荧光传感配合物的设计和筛选提供实验依据.     

Synthesis,Crystal Structure and Characterization of a New Coordination Polymer Based on Trinuclear Mn（Ⅱ） Cluster：[Mn3（L）2（adip）3]·2H2O

The coordination polymer,[Mn3(L) 2(adip) 3]·2H2O(L = 2-(4-fluorophenyl) -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid) ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1 with a = 8.4085(11) ,b = 11.1273(14) ,c = 14.5758(18) ,α = 78.528(2) ,β = 75.425(2) ,γ = 78.143(2) °,V = 1276.0(3) 3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm3,F(000) = 647,μ(MoKa) = 0.819 mm-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn(Ⅱ) clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.     

Potassium ferro-cyanide trihydrate complex catalyzed one-pot synthesis of 2-phenylimidazo[4,5-f][1,10] phenanthroline

Various 2-phenylimidazo[4,5-f][1,10]phenanthrolines were synthesized from potassium ferro-cyanide trihydrate(KFCT) complex catalyzed three component reaction of 1,10-phenanthroiine-5,6-dione,aromatic aldehydes and ammonium acetate at room temperature in excellent isolated yield.This is a simple and straight forward,high yielding,not involving any hazardous or expensive catalyst method.     

Synthesis, Structure and Photoluminescence of a New Cd(Ⅱ)Coordination Polymer Based on 4-(Carboxymethoxy)-benzoic Acid and 1,10-Phenanthroline Derivative

A new 1D coordination polymer, [Cd2(L1)2(L2)2]·H2O (1, H2L1 = 4-(carboxy-methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with a = 9.985(5), b = 10.768(5), c = 12.512(5), α = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V = 1227.4(10) 3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H···O, O-H···N and O-H···O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.     

One-Pot Synthesis and X-Ray Structure of New,Stable Tetrahydropyrrolo [1,2-a][1,10]phenanthrolines with Four Diastereoisomeric Centers

1,10-Phenanthrolinium N-ylides react with ethyl cyanoacetate and aromatic aldehydes via a domino-Knoevenagel cyclization to produce a new class of tetrahydropyrrolo [1,2-a][1,10] phenanthrolines with four diastereoisomeric centers as stable helical compounds in a simple, mild, and efficient protocol in excellent yields. Explicit structural elucidation of compounds was accomplished by single-crystal x-ray diffraction.