烷氧基菲咯啉设计合成及其氮磷杂配铜光敏剂的光解水制氢性能

以功能化氮配体为导向,以4,7-二苯基-1,10-菲咯啉为原料,经季铵化、氧化、卤化和醚化合成了一类新型的2,9-二烷氧基-4,7-二苯基-1,10-菲咯啉配体5a~5e。再以Xantphos为膦配体,通过原位配位方法合成一系列氮磷杂配铜光敏剂（CuPS A~H）,在均相光解水制氢体系中研究其光敏活性。制氢结果表明,以2,9-二乙氧基为较佳取代基,CuPS D的催化产氢总转换数（TON）可达270。在光电物理性能分析中,发现这类杂配铜配合物都有一个相似的氧化还原电位（E^oxd=-0.8 V,E^red=-1.2 V）。具有乙氧取代基的铜配合物CuPS D相对于其他取代基的铜基配合物,荧光最弱,表明乙氧基有助于提高荧光淬灭效率,增强铜光敏剂的光化学转换能力。     

异腈氮杂配铜配合物的合成及光解水制氢性能

设计、合成了供电子性能的异腈二齿配体,可与铜(Ⅰ)和1,10-菲咯啉衍生物发生反应,形成一类异腈氮杂配铜光敏剂4a~4h,并在光解水制氢体系研究了其光催化活性。实验结果表明,2,2′-二异腈基二苯硫醚与2,9位具有取代基的菲咯啉形成的杂配铜配合物具有一定的光敏活性,光解水制氢TON达168。结合这类配合物的光物理性能和光电性能研究,对这类配合物作为光敏剂的构效关系及其内在机理进行了初步地解释与探讨。     

异腈氮杂配铜配合物的合成及光解水制氢性能

设计、合成了供电子性能的异腈二齿配体,可与铜（Ⅰ）和1,10-菲咯啉衍生物发生反应,形成一类异腈氮杂配铜光敏剂4a~4h,并在光解水制氢体系研究了其光催化活性。实验结果表明,2,2''-二异腈基二苯硫醚与2,9位具有取代基的菲咯啉形成的杂配铜配合物具有一定的光敏活性,光解水制氢TON达168。结合这类配合物的光物理性能和光电性能研究,对这类配合物作为光敏剂的构效关系及其内在机理进行了初步地解释与探讨。     

大环芳烃菲咯啉的设计、合成及其铜光敏剂光解水制氢性能

设计、合成了一类4,7位为大环芳烃的菲咯啉二齿氮配体,可与铜.和Xantphos原位配位,获得一系列新型氮磷杂配铜光敏剂CuPS 1～CuPS 6,在均相光解水制氢体系中研究其光敏活性及构效关系。实验结果表明,在菲咯啉4,7位引入芳基有利于提高其光敏活性,1-萘基取代的CuPS 3有最好的制氢活性,光解水制氢转化数(TON)达957。通过理论计算对比分析,1-萘基取代基与菲咯啉母核具有较大的二面角,对铜配合物的激发态有较好的保护作用,因此CuPS 3表现出较高的荧光量子产率(0.036)和较长的激发态寿命(1.36μs)。     

基于双膦配体、氮配体的两个铜(Ⅰ)配合物的合成、光谱学性质和太赫兹时域光谱（英文）

在甲醇和二氯甲烷的混合溶剂中合成了 2个新的铜(Ⅰ)配合物:[Cu(dppp)(Bphen)]Cl·1.8CH_3OH (1)和[Cu_2(CN)_2(dppp)(dmp)_2]·2.5CH_3OH(2) (dppp=1,3-双(二苯基膦基)丙烷,Bphen=4,7-二苯基-1,10-菲咯啉,dmp=2,9-二甲基-1,10-菲咯啉),并通过X射线单晶衍射、元素分析、红外光谱、核磁共振氢谱及磷谱、荧光光谱和太赫兹时域光谱对2个配合物进行了分析和表征。单晶结构表明配合物1是以Cu(Ⅰ)为中心,Bphen和dppp为配体,螯合形成的扭曲四面体结构。配合物2则是由CuCN、dppp和dmp以2:1:2的比例混合得到。配合物2的双膦配体的2个膦基分别与2个Cu(Ⅰ)形成配位键,每个Cu(Ⅱ)又分别与1个氰根和1个dmp配位。发光光谱表明配合物1和2所有的发射峰来源于金属-配体电荷迁移(MLCT)。太赫兹时域光谱对配合物1和2的研究提供了帮助。     

2,9-二甲基-1,10-菲咯啉的dl-丙氨酸衍生物的合成表征及其镧(III)配合物与DNA作用光谱研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了2,9-二甲基-1,10-菲咯啉的dl-丙氨酸衍生物:1,10-菲咯啉-2,9-二亚甲基亚氨基-(2,2'-二甲基)二乙酸(L).该配体经过元素分析、红外光谱、核磁共振氢谱表征.在25±0.1℃、I=0.1mol·dm-3NaNO3的条件下,用pH电位滴定法测定了该配体的质子化常数及其与 La(III)的配合物的稳定常数.通过电子光谱研究了La(III)的配合物与小牛胸腺DNA的相互作用.用溴化乙锭作为荧光探针研究了La(III)-L配合物与小牛胸腺DNA的相互作用的过程.作为对比,也研究了La(III)分别与 1,10-菲咯啉(Phen)、dl-丙氨酸(Ala)的配合物与小牛胸腺DNA的相互作用.结果表明La(III)-L配合物与小牛胸腺DNA作用既有共价键合,又有插入作用.     

2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物的合成表征及其Mn(II),Co(II),Ni(II),Cu(II),Zn(II)配合物稳定性研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物-N,N'-二(2'-吡啶基)甲基-1,10-菲咯啉-2,9-二甲胺(L).该配体经过元素分析、红外光谱、核磁共振氢谱表征.在25±0.1℃、I=0.1mol·dm-3NaNO3的条件下,用pH电位滴定法测定了该配体在水溶液中的质子化常数及其分别与Mn(II),Co(II),Ni(II),Cu(II)和Zn(II)的配合物的稳定常数,提出了配合物的可能结构.进一步讨论了相应稳定常数较大的内在原因.     

2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物的合成表征及其MnⅡ,CoⅡ,NiⅡ,CuⅡ,ZnⅡ配合物稳定性研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了2,9-二甲基-1,10-菲咯啉的α-氨甲基吡啶衍生物-N,N'-二(2'-吡啶基)甲基-1,10-菲咯啉-2,9-二甲胺(L)。该配体经过元素分析、红外光谱、核磁共振氢谱表征。在25±0.1℃、I=0.1mol·dm^-3NaNO₃的条件下,用pH电位滴定法测定了该配体在水溶液中的质子化常数及其分别与Mn(Ⅱ),Co(Ⅱ),Ni(II),Cu(Ⅱ)和Zn(Ⅱ)的配合物的稳定常数,提出了配合物的可能结构。进一步讨     

2,9-二甲基-1,10-菲咯啉的l-缬氨酸衍生物的合成表征及其镧(Ⅲ)配合物与DNA作用光谱研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了1,10-菲咯啉的l-缬氨酸衍生物------1,10-菲咯啉-2,9二亚甲基亚氨基-(2,2'-二异丙基)二乙酸(L)。该配体经过元素分析、红外光谱、核磁共振氢谱表征。通过电子光谱,研究了La(Ⅲ)的配合物与小牛胸腺DNA的相互作用。用溴化乙锭作为荧光探针,还研究了La(Ⅲ)-L配合物与小牛胸腺DNA的相互作用的过程。作为对比,也研究了La(Ⅲ)分别与1,10-菲咯啉(Phen)、l-缬氨酸(Val)的配合物与小牛胸腺DNA的相互作用。结果表明La(Ⅲ)-L配合物与小牛胸腺DNA作用既有共价键合,又有插入作用。     

2,9-二甲基-1,10-菲咯啉的l-缬氨酸衍生物的合成表 征及其镧(Ⅲ)配合物与 DNA作用光谱研究

以2,9-二甲基-1,10-菲咯啉为初始原料,合成了1,10-菲咯啉的l-缬氨酸衍生物------1,10-菲咯啉-2,9二亚甲基亚氨基-(2,2'-二异丙基)二乙酸(L)。该配体经过元素分析、红外光谱、核磁共振氢谱表征。通过电子光谱,研究了La(Ⅲ)的配合物与小牛胸腺DNA的相互作用。用溴化乙锭作为荧光探针,还研究了La(Ⅲ)-L配合物与小牛胸腺DNA的相互作用的过程。作为对比,也研究了La(Ⅲ)分别与1,10-菲咯啉(Phen)、l-缬氨酸(Val)的配合物与小牛胸腺DNA的相互作用。结果表明La(Ⅲ)-L配合物与小牛胸腺DNA作用既有共价键合,又有插入作用。     

Effect of heterocyclic diimine ligands with donor and acceptor substituents on the spectroscopic and electrochemical properties of Au(III) complexes

The composition, structure, and properties of a series of Au(III) complexes with heterocyclic diimine ligands [Au(N^N)Cl₂]⁺, where (N^N) = 2,2′-bipyridine (Bipy), 4,4′-dimethyl-2,2′-bipyridine (DmBipy), 2,2′-biquinoline (Bqx), 1,10-phenanthroline (Phen), 2,9-dimethyl-1,10-phenanthroline (DmPhen), and 4,7-diphenyl-1,10-phenanthroline (DphPhen), were characterized by ¹H NMR, electronic absorption, and emission spectroscopy and also by cyclic voltammetry. The influence of donor and acceptor substituents on the spectroscopic and electrochemical properties of the Au(III) complexes was revealed.     

Bimetallic bis(diphenylphosphino)acetylene bridged copper(I) complexes with 1,10-phenanthroline derivatives: synthesis,crystal structure,and spectroscopic characterization

A new series of bimetallic bis(diphenylphosphino)acetylene-bridged copper(I) 1,10-phenanthroline complexes, [Cu₂(dppa)₂(L)₂](BF₄)₂; L?=?1,10-phenanthroline (1); 4-methyl-1,10-phenanthroline (2); 4,7-dimethyl-1,10-phenanthroline (3); and 2,9-dimethyl-1,10-phenanthroline (4), have been prepared and characterized by spectroscopic methods. The X-ray structures of 1 and 4 were determined. The structures consist of centrosymmetric bimetallic 10-membered chair-like dimetallacycles. In 1, intermolecular C–H?π interactions result in bending of the phenanthroline ligand and sterically induced lengthening of one Cu–P bond. In 1–4, the ³¹P NMR downfield coordination shift, relative to the free ligand, correlates with the basic strength of the 1,10-phenanthroline ligands.     

Mixed-ligand complex formation in the copper(I)-2,9-dimethyl-1,10-phenanthroline-3,3′-bridged biquinoline system as probed by 1H NMR

The interaction of the copper(I) complex of 2,9-dimethyl-1,10-phenanthroline (neocuproine, DMP) with 2,3,8,9-dibenzo-4,7-dimethyl-5,6-dihydro-1,10-phenanthroline (cuprotest, DMQ) in a CD₃OD solution has been studied by ¹H NMR. DMQ is substituted for the DMP ligand in the inner coordination sphere of the Cu⁺ complex. To describe the experimental integrated intensities of NMR signals as a function of concentrations of the components, a model of the process is proposed implying the formation of a heteroleptic complex, which, presumably, has a bridging structure.     

选择性响应Cu~(2+)、Ag~+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)双(2,1-亚苯基)二乙酸酯(探针1);再将其进一步水解得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)二苯酚(探针2)。经1H NMR、13C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu2+、Ag+不同的荧光猝灭作用,探针2还能识别阴离子F-和AcO-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2∶1。     

选择性响应Cu2+、Ag+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）双（2,1-亚苯基）二乙酸酯（探针1）;再将其进一步水解得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）二苯酚（探针2）。经¹H NMR、¹³C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu²⁺、Ag⁺不同的荧光猝灭作用,探针2还能识别阴离子F^-和AcO^-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2：1。     

Synthesis,characterization, and antitumor properties of ruthenium(II) anthraquinone complexes

Three new Ru(II) complexes, [Ru(dmb)₂(ipad)](ClO₄)₂ (dmb = 4,4′-dimethyl-2,2′-bipyridine, ipad = 2-(anthracene-9,10-dione-2-yl) imidazo[4,5-f][1,10]phenanthroline, 1), [Ru(dmp)₂(ipad)](ClO₄)₂ (dmp = 2,9-dimethyl-1,10-phenanthroline, 2), and [Ru(dip)₂(ipad)](ClO₄)₂ (dip = 4,7-diphenyl-1,10-phenanthroline, 3), have been synthesized and characterized. The three Ru(II) complexes intercalate with the base pairs of DNA. The in vitro antiproliferative activities and apoptosis-inducing characteristics of these complexes were investigated. The complexes exhibited cytotoxicity against various human cancer cell lines. BEL-7402 cells displayed the highest sensitivity to 1, accounted for by the greatest cellular uptake. Complex 1 was shown to accumulate preferentially in the nuclei of BEL-7402 cells and cause DNA damage and induce apoptosis, which involved cell cycle arrest and reactive oxygen species generation.     

Synthesis and characterization of manganese(II), nickel(II), copper(II) and zinc(II) Schiff-base complexes derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine

The synthesis of a new Schiff base containing 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine is described. The reaction of 1,10-phenanthroline-2,9-dicarboxaldehyde with 2-mercaptoethylamine leads to 2,9-bis(2-ethanthiazolinyl)-1,10-phenanthroline (I) which undergoes rearrangement when reacted with manganese, nickel, copper or zinc ions to produce complexes of the tautomeric Schiff base 2,9-bis[2-(2-mercaptoethyl)-2-azaethene]-1,10-phenanthroline (L). The [M(L)Cl₂] complexes [where M = Mn(II), Ni(II), Cu(II) and Zn(II) ions] were characterized by physical and spectroscopic measurements which indicated that the ligand is a tetradentate N₄ chelating agent.     

Synthesis of Interlocked Diazacoronand System

Abstract

New 2,9-disubstituted 1,10-phenanthroline derivatives have been obtained, retaining the ability to form stable complexes with transition metals. Due to special, pseudotetrahedral topography of the copper(I) complexes the subsequent ring formation reaction can lead to copper(I) catenates. Thus, the known 2,9-bis(p-hydroxyphenyl)-1,10-phenanthroline ligand, was elongated by the reaction with tert-butyl bromoacetate, forming a diester capable of undergoing a double amidation reaction. Such synthetic strategy can provide the corresponding diazacoronands as well as amide-containing interlocked catenane systems, when a three-dimensional template effect of copper atom is employed.     

Allyl rhodium(III) complexes containing heterocyclic nitrogen ligands

Summary A series of hexacoordinated Rh^III complexes of general formula trans-[RhCl₂(allyl)(N-N)] (allyl = C₃H₅ or C₄H₇; N- = 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,2-bipyridine or 4,4-dimethyl-2,2-bipyridine) have been synthesized and characterized by spectroscopic methods. The complexes have an octahedral geometry with the Cl ligands coordinated in the trans positions. The catalytic activity of [RhCl₂(C₄H₇)(phen)] with respect to hydrogenation of alkenes has been investigated.