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.     

一个新型钌(Ⅱ)配合物对F~-的双重光谱识别

采用紫外-可见光谱和荧光光谱滴定方法研究了钌(Ⅱ)配合物[Ru(bpy)(H2iip)2](ClO4)2[bpy=2,2'-联吡啶,H2iip=2-吲哚基-咪唑并[4,5-f][1,10]-邻菲罗啉]在DMSO溶液中对卤素离子的识别性质.结果表明该配合物能比色和荧光双重光谱高选择性识别F-.     

2-噻吩咪唑[4,5-f][1,10]菲啰啉及其衍生物的顺式镉(Ⅱ)、锰(Ⅱ)和镍(Ⅱ)配合物的结构和波谱研究

本文报道了3个基于2-噻吩咪唑[4,5-f][1,10]菲啰啉(TIP)和2-(5-溴-2-噻吩)咪唑[4,5-f][1,10]菲啰啉(5-Br-TIP)的镉(Ⅱ)配合物1[cis-Cd(TIP)2(NO3)2]、锰(Ⅱ)配合物2[cis-Mn(5-Br-TIP)2Cl2]和镍(Ⅱ)配合物3[cis-Ni(TIP)2Cl(CH3OH)]Cl.CH3OH的合成、波谱和晶体结构表征。它们均为顺式1∶2单核配合物,其中1为8配位,2和3为6配位,TIP和5-Br-TIP配体在不同配合物中噻吩和邻菲啰啉并咪唑环之间的二面角有所不同,但都不大,在3.9(1)°~9.2(1)°范围。     

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.     

配体的空间构型及疏水性对钌（Ⅱ）多吡啶配合物与DNA作用的影响

合成了4－氰基苯基咪唑并[5,6-f]邻菲咯啉（CYIP）和2－羧基苯基咪唑并[5, 6-f]邻菲咯啉（COIP）两种新配体及它们的钌混配配合物[Ru(bpy)2CYIP](ClO4)2 ·H2O（Rul）（bpy=2,2′-联吡啶），[Ru(phen)2CYIP](ClO4)2·H2O(Ru2) (phen=1,10-邻菲咯啉），[Ru(bpy)2COIP](ClO4)2·3H2O(Ru3)和[Ru(phen)2COIP] (ClO4)2·H2O(Ru4)，并用红外光谱、紫外光谱、核磁和质谱对它们进行了表征。 通过循环伏安法研究了这些配合物的电化学性质。采用电子吸收光谱、稳态荧光、 圆二色谱和粘度测定研究了配合物与小牛胸腺DNA的相互作用。结果表明配合物 Rul和Ru2通过CYIP配体以插入的方式与DNA结合，而配合物Ru3和Ru4则通过COIP配 体以部分插入的方式与DNA结合。     

钌多吡啶配合物与DNA作用及抗肿瘤活性

应用电子吸收光谱、荧光光谱和粘度测定等方法研究钌多吡啶配合物[Ru(phen)2(Hecip)]2(phen=1,10-邻菲啰啉,Hecip=2(9-乙基-9H-咔唑-3-基)-1H-咪唑并[4,5-f][1,10]菲啰啉)与DNA相互作用。结果表明配合物与DNA键合计量比为2∶1,键合常数超过105mol-1.L,配合物以插入方式与DNA结合。运用琼脂糖凝胶电泳实验研究配合物诱导pBR322DNA断裂及断裂机理。体外抗肿瘤活性结果表明配合物能有效抑制肿瘤细胞增殖,进一步研究表明配合物可以将细胞周期阻滞在S期。     

一个新型钌(II)配合物对F－的双重光谱识别

采用紫外-可见光谱和荧光光谱滴定方法研究了钌(II)配合物[Ru(bpy)(H2iip)2](ClO4)2 [bpy＝2,2’-联吡啶, H2iip＝2-吲哚基-咪唑并[4,5-f][1,10]-邻菲罗啉]在DMSO溶液中对卤素离子的识别性质. 结果表明该配合物能比色和荧光双重光谱高选择性识别F－.     

1,10-邻菲啰啉衍生物钌配合物的合成、 表征及与DNA和BSA的相互作用

通过2-(4-吡啶)-咪唑[4,5-f]-1,10-邻菲啰啉(L₁)与[Ru(η⁶-cymene)(μ-Cl)Cl]₂反应合成了3种新型芳基钌配合物, 并利用新配体2-(4-咪唑基苯基)咪唑[4,5-f]-1,10-邻菲啰啉(L₂)与RuCl₃反应合成了配合物4. 利用核磁共振波谱、 质谱等对配合物进行了表征. 通过紫外光谱和圆二色谱研究了配合物在缓冲溶液中的稳定性及与CT-DNA的相互作用, 利用荧光光谱研究了配合物与牛血清蛋白的作用, 用乌氏黏度计测试了配合物对DNA黏度的影响, 并通过荧光光谱、 凝胶电泳研究了配合物4在不同pH条件下的荧光响应及与pBR322 DNA的作用. 结果表明, 配合物通过嵌入的方式与DNA作用, 并对DNA的二级结构产生影响; 配合物1~4均可与牛血清蛋白的一个位点发生相互作用并使其发生静态荧光猝灭. 配合物4在光照条件下有活性氧生成, 可以使pBR322 DNA断裂并在酸性溶液中荧光增强.     

一种含芴基的钌(II)配合物的合成及DNA键合性质

合成了一种新的钌(II)配合物[Ru(bpy)2(Hfip)](ClO4)2, 其中bpy代表2,2′-联吡啶, Hfip代表2-(9H-芴-2-基)-1H-咪唑-[4,5-f]-[1,10]-邻菲啰啉. 通过紫外可见光谱、荧光光谱、稳态荧光淬灭、与溴化乙锭的竞争实验、粘度测量和DNA热变性研究了该配合物与小牛胸腺DNA的键合性质. 结果表明, 该配合物能嵌入键合DNA, 键合常数Kb=8.6×105 L·mol-1 (50 mmol·L-1 NaCl).     

噻吩基钌配合物与酵母RNA的相互作用研究

通过紫外-可见吸收光谱和荧光光谱滴定、稳态荧光猝灭以及盐效应实验研究了噻吩基钌配合物[Ru(bpy)2(Htip)]Cl2(1)、[Ru(Htip)2(dppz)]Cl2(2)、[Ru(Htip)3]Cl2(3)和[Ru2(bpy)4(H2bipt)]Cl4(4){bpy=2,2'-联吡啶;Htip=2-噻吩咪唑[4,5-f][1,10]邻菲咯啉;H2bipt=2,5-二(2-咪唑[4,5-f][1,10]邻菲咯啉)噻吩;dppz=二吡啶并[3,2-a:2',3'-c]吩嗪}与酵母RNA(yeast-RNA)的相互作用,并比较了该类配合物与yeast-RNA和小牛胸腺DNA(ct-DNA)的键合性质。结果表明,该类噻吩基钌配合物是较强的RNA嵌入试剂,其中配合物2和3的RNA键合强度大于其DNA键合强度;此系列配合物在低盐和高盐浓度时均能与RNA较强地结合,即使在100 mmol/L Na Cl条件下仍具有较大的RNA键合常数;配合物1与RNA键合时荧光强度下降,配合物2在水溶液中以及与RNA键合时几乎无荧光,而它们与DNA作用时荧光强度明显增大,显示出良好的区分RNA和DNA的荧光特性。     

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.     

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.     

New star-shaped trinuclear Ru(II) polypyridine complexes of imidazo[4,5-f][1,10]phenanthroline derivatives: syntheses, characterization, photophysical and electrochemical properties

A series of new star-shaped trinuclear Ru(II) complexes of imidazo[4,5-f][1,10]phenanthroline derivatives, [{Ru(bpy)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (6), [{Ru(phen)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (7), [{Ru(bpy)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (8), and [{Ru(phen)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (9) [mes(1,4-phO-Izphen)(3) (4) = 2,4,6-tri methyl-1,3,5-tris(4-oxymethyl-1-yl(1H-imidazo-2-yl-[4,5-f][1,10]phenanthroline)phenyl)benzene and (mes(1,2-phO-Izphen)(3) (5) = 2,4,6-trimethyl-1,3,5-tris(2-oxymethyl-1-yl(1H-imidazo-2-yl[4,5-f][1,10]phenanthroline)phenyl)benzene] have been synthesized and characterized. Their photophysical and electrochemical properties have also been studied. The core molecule, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (1) and the trialdehyde intermediate, 2,4,6-trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene (2) are characterized by single crystal X-ray diffraction: triclinic, P1[combining macron]. The complexes 6-9 exhibit Ru(II) metal centered emission at 618, 601, 615, and 605 nm, respectively, in fluid solution at room temperature. The emission profile and emission maxima are similar and independent of the excitation wavelength for each complex. The complexes 6-9 undergo metal centered oxidation and the E(1/2) values for the Ru(II)/Ru(III) redox couples are 1.33, 1.34, 1.35, and 1.35 V versus Ag/Ag(+), respectively, which are cathodically shifted with respect to that of the mononuclear complex [Ru(bpy)(2)(PIP)](2+) (PIP = 2-phenylimidazo[4,5-f][1,10]phenanthroline). The study demonstrates the versatility of the highly symmetric trinucleating imidazo[4,5-f][1,10]phenanthroline-based core ligands 4 and 5 in forming trinuclear Ru(II) complexes.     

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。     

Ruthenium(II) complexes of 2-phenylimidazo[4,5-f] [1,10]phenanthroline. Synthesis,characterization and third order nonlinear optical properties

Three Ru^II complexes [Ru(bpy)₂(PIP)]²⁺, [Ru(PIP)₂(bpy)]²⁺ and [Ru(PIP)₃]²⁺ (PIP = 2-phenylimidazo[4,5-f][1,10]phenanthroline, bpy = 2,2-bipyridine) were prepared and characterized by electrospray mass spectrometry, ¹H-n.m.r, u.v.–vis. and electrochemistry. The nonlinear optical properties (NLO) of the Ru^II complexes were investigated by Z-scan techniques with 12 ns laser pulses at 540 nm, and all of them exhibit both NLO absorption and self-defocusing effects. The corresponding effective NLO susceptibility |³| of the complexes is in the (4.15 – 4.86) × 10^–12 e.s.u. range.     

以2-(2-吡啶基)苯并噻吩为主配体的两种蓝紫光二价铂配合物的合成与性质

以2-(2-吡啶基)苯并噻吩(2-(2-pyridyl)benzothiophene,btp)作为主配体,分别以邻二氮菲[1,10]并咪唑联苯酚(2-(1Himidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol,ipap)和3-甲基-6-苯基咪唑[2,1-b]噻唑(3-Methyl-6-phenylimidazo[2,1-b]thiazole,mpmt)作为辅助配体,成功合成了2个二价铂配合物[(btp)Pt(ipap)]Cl与(btp)Pt(mpmt)Cl,并得到了配合物(btp)Pt(mpmt)Cl的晶体结构。由金属-配体电荷转移引起的2种配合物发光,具有60%左右的内量子效率,发射峰在426 nm(蓝色)与381 nm(紫色)处。HOMO/LUMO轨道能级分别为-4.69 eV/-2.55 eV与-4.80 eV/-2.21 eV。单晶衍射结果表明,较低的共轭程度导致了该类配合物的短波长发射。     

Experimental and Theoretical Studies on DNA‐Binding and Spectral Properties of ‘Light Switch’ Complexes [Ru(L)2(ppn)]2+ (L=2,2′‐Bipyridine and 1,10‐Phenanthroline; ppn=Pteridino[6,7‐f] [1,10]phenanthroline‐11,13‐diamine)

The ligand pteridino[6,7‐f] [1,10]phenanthroline‐11,13‐diamine (ppn) and its Ru^II complexes [Ru(bpy)₂(ppn)]²⁺ ( 1 ; bpy=2,2′‐bipyridine) and [Ru(phen)₂(ppn)]²⁺ ( 2 ; phen=1,10‐phenanthroline) were synthesized and characterized by elemental analysis, electrospray MS, ¹H‐NMR, and cyclic voltammetry. The DNA‐binding behaviors of 1 and 2 were studied by spectroscopic and viscosity measurements. The results indicate that both complexes strongly bind to calf‐thymus DNA in an intercalative mode, with DNA‐binding constants K_b of (1.7±0.4)?10⁶ M ^?1 and (2.6±0.2)?10⁶ M ^?1, respectively. The complexes 1 and 2 exhibit excellent DNA‐‘light switch’ performances, i.e., they do not (or extremely weakly) show luminescence in aqueous solution at room temperature but are strongly luminescent in the presence of DNA. In particular, the experimental results suggest that the ancillary ligands bpy and phen not only have a significant effect on the DNA‐binding affinities of 1 and 2 but also have a certain effect on their spectral properties. [Ru(phen)₂(ppn)]²⁺( 2 ) might be developed into a very prospective DNA‐‘light switch’ complex. To explain the DNA‐binding and spectral properties of 1 and 2 , theoretical calculations were also carried out applying the DFT/TDDFT method.     

Investigation of DNA/BSA binding of three Ru(II) complexes by various spectroscopic methods,molecular docking and their antimicrobial activity

An intercalative ligand, ppip (ppip = {2-(4-(piperidin-1-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline}), and its mononuclear Ru(II) polypyridyl complexes, [Ru(phen)₂(ppip)]²⁺ (1) (phen=1,10-phenanthrolene), [Ru(bpy)₂(ppip)]²⁺ (2) (bpy=2,2′-bipyridine) and [Ru(dmb)₂(ppip)]²⁺ (3) (dmb=4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized by elemental analysis and spectroscopic techniques such as UV–vis, IR, ¹H, as well as ¹³C NMR and ESI-MS. The interaction of these complexes with DNA/BSA (bovine serum albumin) was investigated using absorption, emission spectroscopy, viscosity measurements and molecular docking studies. The docking study infers that the binding strength (K_b) of these complexes was in agreement with results from absorption and emission techniques. These studies reveal that these three Ru(II) polypyridyl complexes bind to DNA/BSA. The binding ability of these complexes in the presence of different ions and solvents were also reported. All complexes were effectively cleaving pBR322 DNA in different forms and follows order which is similar to absorption and emission studies. These complexes were effective exhibiting the antimicrobial activity against different microbes Bacillus subtilis, Escherichia coli and Staphylococcus aureus.     

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.