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,characterization, and DNA binding of ruthenium(II) complexes with 2-benzo[b] furan-2-yl-1H-imidazo[4,5f][1,10]phenanthroline as an intercalative ligand

DNA-binding properties of a number of ruthenium complexes with different polypyridine ligands are reported. The new polypyridine ligand BFIP (=2-benzo[b] furan-2-yl-1H-imidazo[4,5-f][1,10]phenanthroline) and its ruthenium complexes [Ru(bpy)₂BFIP]²⁺ (bpy = 2,2′-bipyridine), [Ru(dmb)₂BFIP]²⁺ (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Ru(phen)₂BFIP]²⁺ (phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, mass spectra, IR, UV-Vis, ¹H- and ¹³C-NMR, and cyclic voltammetry. The DNA binding of these complexes to calf-thymus DNA (CT-DNA) was investigated by spectrophotometric, fluorescence, and viscosity measurements. The results suggest that ruthenium(II) complexes bind to CT-DNA through intercalation. Photocleavage of pBR 322 DNA by these complexes was also studied, and [Ru(phen)₂BFIP]²⁺ was found to be a much better photocleavage agent than the other two complexes.     

Synthesis,DNA‐Binding and Photocleavage Studies of the Ruthenium(II) Complexes [Ru(phen)2(ppd)]2+ and [Ru(phen)(ppd)2]2+ (ppd=Pteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione,phen=1,10‐Phenanthroline)

Two new complexes, [Ru(phen)₂(ppd)]²⁺ ( 1 ) and [Ru(phen)(ppd)₂]²⁺ ( 2 ) (ppd=pteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione, phen=1,10‐phenanthroline) were synthesized and characterized by ES‐MS, ¹H‐NMR spectroscopy, and elemental analysis. The intercalative DNA‐binding properties of 1 and 2 were investigated by absorption‐spectroscopy titration, luminescence‐spectroscopy studies, thermal denaturation, and viscosity measurements. The theoretical aspects were further discussed by comparative studies of 1 and 2 by means of DFT calculations and molecular‐orbital theory. Photoactivated cleavage of pBR322 DNA by the two complexes were also studied, and 2 was found to be a much better photocleavage reagent than 1 . The mechanism studies revealed that singlet oxygen and the excited‐states redox potentials of the complex may play an important role in the DNA photocleavage.     

Thiosemicarbazone Complexes of Ruthenium(II) and Rhodium(I) Containing Triphenylphosphine

Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh ₃ ) ₂ (TSC)], [RuH(CO)(PPh ₃ ) ₂ (TSC)], and [Rh(PPh ₃ ) ₃ (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh ₃ ) ₃ ], [RuH ₂ (CO)(PPh ₃ ) ₃ )], and [RhH(PPh ₃ ) ₄ ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, ¹ H NMR, ³¹ P NMR, and electronic spectral data.     

具有三维结构的Co(II)配合物二阶非线性光学性质的DFT研究

以实验合成出的Schiff碱配体和Co(II)配合物为母体,设计了Schiff碱配体和具有三维结构的Co(II)配合物.采用密度泛函理论的B3LYP/6-31g(d)-FF方法对具有开壳层电子组态Co(II)配合物及相应配体的二阶非线性光学(NLO)效应进行了计算.结果表明:Schiff碱配体形成配合物后分子的二阶NLO性质没有发生大的改变,这是由于金属Co2 离子在配合物电荷转移(CT)过程中起到了桥的作用,对分子的二阶NLO响应直接贡献不大.结合配合物的前线分子轨道分析发现,在分子内电荷转移过程中,对分子二阶NLO系数的主要贡献是配体内电荷转移(ILCT)跃迁.     

单齿配体取代基对钌(Ⅱ)芳烃配合物光致配体解离能力的影响

合成了三种钌(Ⅱ)芳烃配合物[(η⁶-p-cymene)Ru(bpy)(py-R)]²⁺(bpy=2,2′-联吡啶,py=吡啶,R=N(CH₃)₂,H,NO₂),通过紫外-可见吸收光谱、核磁共振、高分辨质谱及DNA凝胶电泳等手段研究了单齿配体吡啶对位取代基的推拉电子能力如何影响配合物的光致配体解离能力。研究发现,当单齿配体吡啶对位取代基为拉电子基团硝基时,配合物具有光致单齿配体解离能力及潜在的光活化抗肿瘤活性。     

Bis(4,4′‐dimethyl‐2,2′‐bipyridine) ruthenium (II) Complexes Containing 2‐Arylimidazo‐ [4,5‐f] [1,10] phenanthroline: Syntheses,Characterization and Third‐order Nonlinear Optical Properties

Four novel mononuclear ruthenium(II) complexes [Ru(dmb)₂L]²⁺ [dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, L = imidazo‐[4,5‐f][1,10]phenanthroline (IP), 2‐phenylimidazo‐[4,5‐f][1,10]phenanthroline (PIP), 2‐(4′‐hydroxyphenyl)imidazo‐[4,5‐f] [1,10] phenanthroline (HOP), 2‐(4′‐dimethylaminophenyl) imidazo‐[4, 5‐f] [1,10] phenanthroline (DMNP)] were synthesized and characterized by ES‐MS, ¹H NMR, UV‐vis and electrochemistry. The nonlinear optical properties of the ruthenium(II) complexes were investigated by Z‐scan techniques with 12 ns laser pulse at 540 nm, and all of them exhibit both nonlinear optical (NLO) absorption and self‐defocusing effect. The corresponding effective NLO susceptibility |x³| of the complexes is in the range of 2.68 × 10^?12‐4.57 × 10^?12 esu.     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(BPIP)] and [Ru(phen)2(BPIP)] (BPIP = 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline)

New ligand 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and its complexes [Ru(bpy)₂(BPIP)]²⁺ (1) (bpy = 2,2′-bipyridine) and [Ru(phen)₂(BPIP)]²⁺ (2) (phen = 1,10-phenanthroline) have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. The interaction of two Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by spectroscopic and viscosity measurements. Results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 2 is much greater than that of complex 1. Furthermore, when irradiated at 365 nm, both complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA.     

Synthesis, characterization and DNA-binding studies of ruthenium(II) mixed-ligand complexes containing dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline

A novel ligand dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (dpoq) and its complexes [Ru(bpy)₂(dpoq)]²⁺ and [Ru(phen)₂(dpoq)]²⁺ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, electrospray mass spectra and ¹H NMR. The interaction of Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, thermal denaturation and viscosity measurements. Results suggest that two Ru(II) complexes bind to DNA via an intercalative mode.     

一系列Ru(II)配合物电致化学发光性质的比较研究

比较研究了以C₂O₄^2－为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)₂L¹]^2＋, [Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋, [Ru(phen)₂L¹]^2＋和[Ru(phen)₂L²]^2＋(其中bpy＝2,2′-联吡啶, phen＝1,10-邻菲啰啉, L¹＝4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L²＝3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L³＝3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋和[Ru(phen)₂L²]^2＋的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)₃]^2＋相差不大.     

钌(II)多吡啶配合物与DNA相互作用研究*

DNA是遗传信息的携带者和基因表达的物质基础,金属配合物与DNA的相互作用研究已受到广泛关注,成为生物无机化学的重要研究内容之一。本文简要评述了钌(II)多吡啶配合物在DNA识别、断裂及拓扑异构酶抑制方面的研究情况。     

Synthesis,Crystal Structure and Nonlinear Optical Properties of a new cluster compound: MoS4Cu3(PyPPh2)3Cl

Reaction of [NH₄]₂[MoS₄], CuCl and PyPPh₂ in the solid state produces a cube-like cluster. The cluster crystallizes in the orthorhombic space group P2₁2₁2₁ with four formula units in a cell of dimensions a = 12.8980(10) , b = 17.6820(10), c = 22.665(2) Å. Anisotropic refinement for all nonhydrogen atoms yielded the values R = 0.0397 and R _w = 0.1185 for 8803 observed reflections. The structure is built up from three [Cu(Ph₂PPy)]⁺ units bridged by MoS^2? ₄ to form a tetranuclear symmetrical cube-like molecule. Investigation of the third-order optical nonlinear value showed that it exhibits a considerable nonlinear absorptive and self-defocusing effect with α₂ = 1.3 × 10^?11 m w^?1 and n ₂ = ? 3.2 × 10^?18 m² w^?1 in a 1.5 × 10^?4 M DMF solution.     

杯[4]芳烃修饰的钌(II)配合物的合成与性质

合成了一种新颖的杯[4]芳烃修饰的钌（Ⅱ）配合物[Ru₂（bpy）₄（H₂L）]（ClO₄）₄（1）（bpy=2,2''-联吡啶,H₂L=11,23-双（2-咪唑[4,5-f]-1,10-菲啰啉）-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃）,并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液（1∶100,V/V）中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的“off-on-off”型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F^-和OAc^-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。     

新型三齿多吡啶钴(II)、钌(II)配合物的合成、表征及其与DNA的作用研究

合成了两种新型三齿多吡啶钴(II)和钌(II)的混配配合物[Co(TolylTPy)(H₂Bzimpy)]Cl₂ [TolylTPy＝4'-对甲基苯 基-2,2':6',2'-三联吡啶, H₂Bzimpy＝2,6-二(苯并咪唑-2)吡啶] (A)和Ru(TolylTPy)(Bzimpy) (B). 用元素分析, IR, ¹H NMR等对它们进行了表征, 测定了配合物B的晶体结构, 用电子吸收光谱、荧光光谱等研究了配合物与小牛胸腺DNA(CTDNA)的相互作用及其对pBR322 DNA的断裂作用. 结果表明, 配合物A和B与CTDNA的作用属静电结合, 凝胶电泳实验说明配合物A在310 nm光辐射15 min, 可使超螺旋pBR322 DNA断裂为开环缺口型和线型DNA.     

Synthesis and Characterization of a Series of Water Soluble Amidomalonato-(lR,2R-Cyclohexanediamine)Platinum(II) Complexes

Abstract

A new series of water soluble platinum(II) complexes of the type [Pt(DACH)[R-CH(COO)₂]], wherein DACH represents IR,2R-cyclohexanediamine and R represents formamido. acetamido, (penta-O-acctyl-gluconyl)amino, and gluconylamino have been synthesized. The modes of binding of amidodicarboxylic acid derivatives in these complexes have been determined by various spectroscopic techniques: ¹H, ¹³ C, and ¹⁹⁵PtNMR; 2D-COSY{¹H-¹H} and 2D-HETCOSY{¹H-¹³C} NMR, MS(FAB), IR and conductivity measurements.     

2-(3-吡唑基)咪唑并[4,5-f]邻菲咯啉的合成

以邻菲咯啉-5,6二-酮和3醛-基吡唑为原料,合成了一种新的配体——2-(3吡-唑基)咪唑并[4,5-f]邻菲咯啉(1),其结构经1H NMR,IR及MS表征。研究了1的电子吸收和荧光性质。     

Synthesis,Structure and Properties of a Zinc(II) Complex with the Lapacholate Anion and Ethanol as Ligands

The reaction of lapachol, 2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphtoquinone, C₁₅H₁₄O₃, with zinc acetate, in ethanol, produces a chelate formula Zn(C₁₅H₁₃O₃)₂(C₂H₆O)₂, whose structure has been determined by single crystal X-ray diffraction. It pertains to the triclinic system, space group P I (No. 2), a = 8.2380(3) Å, b = 9.4900(2) Å, c = 11.0110(4) Å, α = 112.536(2)°, β = 91.204(2)°, γ = 92.664(2)°, Z = 1. Some spectroscopic and chemical properties of the complex are also reported.     

钌配合物[Ru(bpy)2(PNT)]2+的合成、表征及与DNA相互作用研究

以cis-Ru(bpy)2Cl2·2H2O与PNT为原料合成钌(Ⅱ)多吡啶配合物[Ru(bpy)2(PNT)]2+(bpy=2,2’-联吡啶, PNT=2-[4’-(5-四唑基)苯基]咪唑-[4,5-f][1,10]邻菲咯啉), 通过元素分析、质谱和核磁共振波谱对该化合物进行了结构表征. 利用紫外-可见吸收光谱、荧光光谱、热变性和黏度实验研究了配合物与CT-DNA的相互作用, 实验结果表明, 该配合物以部分插入模式与DNA结合.     

Synthesis,Structure and Properties of an Oxalato-Bridged Dinuclear Nickel(II) Complex

A new dinuclear nickel(II) compound, [Ni₂(TPA)2(μ-C₂O₄)](H₂O)_0.75(ClO₄)₂ [TPA = tris(2-pyridylmethyl) amine], was synthesized and characterized by electronic spectroscopy and X-ray methods. In the complex, the oxalate ion acts as a bis-bidentate ligand and the two Ni(II) ions are six coordinated with a distorted octahedral structure. The complex crystallizes in the triclinic space group P_i , with a = 13.203(4), b = 16.574(5), c = 21.802(6) Å, α = 78.644(5), β = 80.299(5), γ = 72.446(5)°, V = 4429 ų, Z = 2; R ₁ = 0.0615, wR ₂ = 0.1639. In the temperature range 4-300 K, magnetic measurements show that the exchange interaction between the two metal ions is antiferromagnetic with J = ? 18.74 cm^?1, g = 2.10.     

Syntheses,Spectroscopy and Calculated Second-Order Nonlinear Optical Properties of a New Series of Square-Pyramidal Substituted Phenylthiourea Zinc(II) Complexes

A new series of square-pyramidal coordination compounds L·Zn(acac)₂ (acac = acetylacetonate; L is a variety of substituted phenylthioureas: p-N,N ′-dimethylaminophenylthiourea 1, p-methoxy-phenylthiourea 2, p-nitrophenylthiourea 3, p-acetylphenylthiourea 4) have been synthesized and characterized by ¹H NMR and IR spectra and elemental analysis. Most of these compounds exhibit wide transparent ranges in the visible region. Their electronic spectra have been studied experimentally, and theoretically by ZINDO/S calculation. The MOPAC software package has been used to evaluate their first-order molecular hyperpolarizabilities (β). All β values of the four coordination compounds are greater than or equal to those of p-nitroaniline, and are larger than β values of their corresponding substituted phenthylthiourea ligands.