Coordination Modes of Polypyridyl Quinoxaline with Hg(Ⅱ),Pb(Ⅱ),Co(Ⅱ)and Mn(Ⅱ)

The interaction of metal ions（Hg^2＋,Pb^2＋,Co^2＋,Mn^2＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ） was investigated,and four new complexes have been synthesized and characterized.Complex 1 exhibits a 0dimensional dual-core structure,2 is a one-dimensional chain structure based on a dual-core Pb unit,while 3 and 4 show a 0 dimensional single-core structural unit.Complex 1 is of monoclinic system,space group C2/c with a = 19.211（4）,b = 23.896（5）,c = 12.698（3） A°,β= 120.11（3）°,V= 5043.0（17）A°3,Z = 4,S = 1.053,F（000） = 2976,R^a = 0.0637 and wR^b = 0.1068（I 〉 2σ（I））.Complex 2 adopts triclinic system,space group P1 with a = 10.370（2）,b = 12.195（2）,c = 21.033（4） A°,α = 80.87（3）,β= 81.22（3）,γ = 82.38（3）°,V= 2579.3（8） A°3,Z = 2,S = 1.099,F（000） = 1328,R^a = 0.0609 and wR^b =0.1365（I 〉 2σ（I））.Complex 3 is of monoclinic system,space group Cllc with a = 14.166（3）,b =16.621（3）,c = 20.248（4） ？,β = 92.18（3）°,V= 4764.0（16） A°3,Z = 4,S = 1.005,F（000） = 2108,R^a =0.0589 and wR^b = 0.1332（I 〉 2σ（I））.Complex 4 belongs to the monoclinic system,space group C2/c with a = 14.404（3）,b = 16.626（3）,c = 20.346（4） ？,β = 92.43（3）°,V= 4868.2（17） A°3,Z = 4,S= 1.068,F（000） = 2108,R^a = 0.0833 and wR^b = 0.1591（I 〉 2σ（I））.Furthermore,the behavior of HPDQ with Hg^2＋,Pb^2＋,Co^2＋ and Mn^2＋ in the solution was also investigated,and the result shows after the metal ions were added respectively,the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.

Micellar Effect on Photoinduced Electron Transfer Reactions of Ruthenium(II) Polypyridyl Complexes with Quinones: Effect of CTAB

Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The complexes have the absorption and emission maximum in the range 452 - 468 nm and 594 - 617 nm respectively. The static nature of quenching is confirmed from the ground state absorption studies. The association constants for the complexes with quinones are calculated from the Benesi-Hildebrand plots using absorption spectral data. The value of quenching rate constant (kq) is highly sensitive to the nature of the ligand and the quencher, the medium, structure and size of the quenchers. Compared to the aqueous medium, the electron transfer rate is altered in CTAB medium. The oxidative nature of the quenching is confirmed by the formation of Ru3+ ion and quinone anion radical.

Crystal Structure and Spectroscopic Analysis of Polypyridyl Quinoxaline with Ce(Ⅲ) and Nd(Ⅲ)

Two high coordination crystals were obtained by the interaction of Ce^（3＋） and Nd^（3＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ）, and they were characterized. Complex 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce（Ⅲ） atoms being ten-, eleven- and twelve-coordinated. Complex 2 is a 0 dimensional dual-core structure and the Nd（Ⅲ） atom is ten-coordinated. Complex 1 is of monoclinic system, space group P2/c with a = 16.850（3）, b = 16.617（3）, c = 24.017（5） ？, β = 100.94（3）o, V = 6602（2） ？~3, Z = 4, S = 1.062, F（000） = 3372, R = 0.0504 and wR = 0.1463（I 〉 2σ（I））. Complex 2 adopts a monoclinic system, space group C2/c with a = 25.795（5）, b = 20.166（4）, c = 13.059（3） ？, β = 112.29（3）°, V = 6286（2） ？~3, Z = 4, S = 1.004, F（000） = 2664, R = 0.0663 and wR = 0.1821（I 〉 2σ（I））. Furthermore, the behaviors of HPDQ with Ce^（3＋） and Nd^（3＋） in the solution are also investigated. After the Ce^（3＋） is added, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd^（3＋）, the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce^（3＋）. However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand.

DNA structure, binding mechanism and biology functions of polypyridyl complexes in biomedicine

There is considerable research interest and vigorous debate about the DNA binding of polypyridyl complexes including the electron transfer involving DNA. In this review, based on the fluorescence quenching experiments, it was proposed that DNA might serve as a conductor. From the time-interval CD spectra, the different binding rates of Δ- and Λ-enantiomer to calf thymus DNA were observed. The factors influencing the DNA-binding of polypyridyl complexes, and the potential bio-functions of the complexes are also discussed.

New Amphiphilic Polypyridyl Ruthenium（Ⅱ） Sensitizer and Its Application in Dye-Sensitized Solar Cells

Amphiphilic polypyridyl mthenium（Ⅱ） complex cis-di（isothiocyanato）（4,4＇-di-tert-butyl-2,2＇-bipyridyl）（4,4＇- dicarboxy-2,2＇-bipyridyl）ruthenium（Ⅱ）（K005） has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer （MLCT） bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru（dcbpy）2（NCS）2, known as the N3 dye, and the amphiphilic ruthenium（Ⅱ） dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode （SCE） with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte.

A Novel Cobalt(III) Mixed-polypyridyl Complex: Synthesis, Characterization and DNA Binding

A novel complex [Co(phen)2HPlP]Cl3[phen= phenanethroline, HPIP=2-(2-hydroxyphenyl) imidazo [4,5-f][l,10]phenanethroline] has been synthesized and structurally characterized by elemental analysis, UV, IR and 1H NMR spectroscopies. The interaction of the complex with calf thymus DNA (CT DNA) has been studied using absorption and emission spectroscopy, DNA melting techniques and cyclic voltammetry. The compound shows absorption hypochromicity, fluorescence enhancement and DNA melting temperature increment when binding to CT DNA. CV measurement shows a shift in reduction potential and a change in peak current with addition of DNA. These results prove mat the compound inserts into DNA base pairs. The shift of peak potential indicates the ion interaction mode between the complex and DNA. The binding constant of the compound to DNA is 4.37 × 104. The complex also seems to be an efficient photocleavage reagent.

手性铱(钌)配合物在不对称催化反应中的应用进展

近年来,将手性八面体金属配合物用于不对称催化引起科学家们的广泛关注。手性八面体金属配合物根据配体是否具有手性可划分为手性仅来源于金属中心及手性来源于手性配体和金属中心的八面体金属配合物。本文介绍并归纳了手性环金属铱(Ir)和钌(Ru)配合物的设计与合成方法,即通过改变金属中心、配体的结合以及配体构型等对其进行调控。随后详细阐述了其在不对称催化中的应用,并根据催化方式不同将应用分为金属配位催化和配体球调控催化。金属配位催化包括多种有机不对称催化,以及可见光诱导多功能催化剂协同不对称催化。配体球调控催化主要用于烯烃加成反应。最后对手性八面体配合物作为配位超分子的建筑单元及其在不对称催化中的应用进行了展望,将二者优势结合有望实现更广泛的应用前景。

配体形状对多吡啶铜(Ⅱ)配合物与DNA作用的影响

合成了一系列含有平面配体的Cu髤多吡啶配合物[Cu(IP)2]2+、[Cu(PIP)2]2+、[Cu(DPPZ)2]2+和[Cu(HPIP)2]2+,用吸收光谱、CD光谱和粘度等方法研究了这些配合物与小牛胸腺DNA的作用。结果表明配体上的取代基及配体的平面性对这些四面体配合物与DNA的结合强弱产生一定的影响。[Cu(DPPZ)2]2+与DNA的结合较强,而[Cu(HPIP)2]2+与DNA的结合较弱。CD光谱显示配合物[Cu(DPPZ)2]2+、[Cu(PIP)2]2+和[Cu(HPIP)2]2+的加入会导致DNA的CD光谱减弱。而[Cu(IP)2]2+的加入则会使DNA的CD光谱增强。同时,[Cu(IP)2]2+与DNA结合后,还会引起一定程度的DNA构型转换,即DNA从B型转换成Z型。

新型双核配合物的形成、与DNA的作用机制及荧光性质研究

利用紫外、荧光和粘度等方法研究了含不同配体的钌(II)配合物[Ru(phen)2CImP]2+(CImP=3,4-二羟基-咪唑并[4,5-i][1,10]邻菲咯啉)和[Ru(phen)2TPPZ]2+(TPPZ=四吡啶[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]吩嗪)与DNA的作用机制,并研究了配合物与Zn2+配合后荧光性质变化.结果表明[Ru(phen)2TPPZ]2+与DNA以插入模式作用,而[Ru(phen)2CImP]2+与DNA则以沟面结合模式作用.向配合物溶液中滴加Zn2+后,配合物[Ru(phen)2TPPZ]2+和[Ru(phen)2CImP]2+均可以与Zn2+形成双核配合物[Ru(phen)2(TPPZ)Zn]4+和[Ru(phen)2(CImP)Zn]4+,配合物的荧光减弱.与DNA作用后,配合物仍可以与Zn2+配位形成双核配合物,但[Ru(phen)2(TPPZ)Zn]4+保持插入模式与DNA作用,配合物的荧光减弱.而[Ru(phen)2(CImP)Zn]4+与DNA则由沟面结合改为插入结合,配合物的荧光增强.

钌多吡啶配合物的合成及插入配体的位阻效应对键合DNA的影响

合成了２，３－二甲基－１，４，８，９－四氮三联苯（ｄｍ ｔａｔｐ）和２，３－二苯基－１，４，８，９－四氮三联苯（ｄｐｔａｔｐ）两种新配体及它们与 ２，２′－联吡啶和钌（Ⅱ）的混配物［Ｒｕ（ｂｐｙ）２ｄｍ ｔａｔｐ］２＋ （１）和［Ｒｕ（ｂｐｙ）２ｄｐｔａｔｐ］２＋ （２）， 用电子吸收光谱、稳态荧光、粘度测定和圆二色谱研究了配合物与小牛胸腺ＤＮＡ的相互作用． 结合我们以前对配合物［Ｒｕ（ｂｐｙ）２ｔａｔｐ］２＋ （３） （ｔａｔｐ 为１，４，８，９－四氮三联苯）与小牛胸腺ＤＮＡ的作用研究， 得出配合物与ＤＮＡ的键合强度顺序为： ［Ｒｕ（ｂｐｙ）２ｔａｔｐ］２＋ ＞［Ｒｕ（ｂｐｙ）２ｄｐｔａｔｐ］２＋ ＞ ［Ｒｕ（ｂｐｙ）２ｄｍ ｔａｔｐ］２＋ ， 这与插入配体的位阻效应的减少趋势相一致． 同时，还测定了配合物与ＤＮＡ的键合常数．

不同配体对钌多吡啶配合物与DNA的作用和荧光性质的影响

Two polypyridyl ligands DCHIP (2 hydro 3,5 dichlorophenyl imidazo phenanthroline),MDHIP(2,4 dihydrophenyl imidazophenanthroline) and their ruthenium?complexes [Ru(phen)2 MDHIP]2+and [Ru(phen)2DCHIP]2+were prepared. Their DNA binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode, but [Ru(phen)2DCHIP]2+exhibited stronger binding affinity for DNA than [Ru(phen)2 MDHIP]2+due to the different planarities and steric effects of ligands. On the other hand, after binding to DNA, the fluorescence intensity of [Ru(phen)2MDHIP]2+decreased, while the fluorescence intensity of [Ru(phen)2 DCHIP]2+increased.

钌(Ⅱ)多吡啶配合物的合成、荧光性质及与脱氧核糖核酸DNA的作用机制研究

设计合成含多个配位中心的多吡啶配体ODCIP(3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(Ⅱ)多吡啶配合物[Ru(bpy)2ODCIP]2+.运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征.利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2+与DNA(脱氧核糖核酸)的作用机制、与Co2+配位后与DNA的作用机制及其荧光变化情况.结果表明[Ru(bpy)2ODCIP]2+与DNA通过部分插入模式作用,[Ru(bpy)2ODCIP]2+与Co2+配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4+也能与DNA插入结合.进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2+和双核配合物[Ru(bpy)2(ODCIP)Co]4+的荧光性质.

新型双核配合物的形成及荧光性质研究

利用光谱学方法研究了[Ru(bpy)2TPPHZ]2+(TPPHZ=四吡啶[3,2-a:2′,3′-c:3″,2″-h:2,3-j]吩嗪)和[Ru(bpy)2ODHIP]2+(ODHIP=3,4-二羟基-咪唑并[4,5-f][1,10]邻菲咯啉)与Ni2+的配位情况及配位后的荧光性质变化,探讨了配合物与Ni2+配位形成双核配合物后与DNA的作用机制变化.结果表明,[Ru(bpy)2TPPHZ]2+和[Ru(bpy)2ODHIP]2+均可与Ni2+配位,形成双核配合物[Ru(bpy)2(TPPHZ)Ni]4+和[Ru(bpy)2(ODHIP)Ni]4+,配合物的荧光强度随着Ni2+浓度的增加而减弱.与DNA作用后,配合物仍可与Ni2+配位形成双核配合物,[Ru(bpy)2(TPPHZ)Ni]4+的荧光几乎完全消失,同时配合物与DNA保持插入模式作用,而配合物[Ru(bpy)2(ODHIP)Ni]4+与DNA的作用则由沟面结合改为插入结合,同时配合物的荧光减弱.

钌(II)多吡啶配合物光断裂DNA的实验研究

研究了一系列钌(II)多吡啶配合物对pBR322DNA的光断裂作用,并与光谱法和粘度法的研究结果进行了对比.实验结果表明,钌(II)多吡啶配合物光断裂DNA的能力不仅与配合物与DNA相互作用的结合模式和结合强度有关,还与配合物自身的电子结构有关;钌(II)多吡啶配合物对DNA的光断裂存在立体选择性;其断裂机理是激发态的配合物与溶液中的氧分子发生能量转移生成单线态氧活性氧化物种,将鸟嘌呤碱基氧化而导致DNA断裂.本研究对于遗传工程中的化学核酸酶以及以DNA为靶标的药物设计有重要的意义.

新型多吡啶配体的设计及其对配合物与DNA作用机制的影响

Two structurally related polypyridyl ligands ODHIP(3,4-dihydroxyl-imidazophenanthroline), MDHIP(2,4-dihydroxyl-imidazo phenanthroline) and their ruthenium(II) complexes [Ru(phen) 2ODHIP] 2+ and [Ru(phen) 2MDHIP] 2+ were prepared and characterized. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the two complexes are bound to DNA by different modes due to the different planarities of ligands. For the complex [Ru(phen) 2MDHIP] 2+, the 2- position ortho group of MDHIP could form an intramolecular hydrogen bond with the nitrogen atom of the imidazole ring to extend the planarity and strengthen the binding affinity. On the other hand, the 4- position ortho group hindered the complex from intercalating into the base pairs of DNA, and finally, making the complex bind to DNA by a partial intercalative mode. However, for the complex [Ru(phen) 2ODHIP] 2+, there was no intramolecular hydrogen bond formed and the two ortho groups further increased the steric effect and decreased the binding affinity, thus making the complex bind to DNA by groove binding mode.

[Ru(bpy)_2tpphz]^(2+)与Zn^(2+)形成的双核配合物的荧光性质研究

The formation of heterobimetallic ruthenium?complex was investigated by absorption and emission spectra. As an intercalator of DNA, the luminescent monometallic ruthenium?complex [Ru(bpy)2tpphz]2+could coordinate with Zn2+to form the nonluminescent heterobimetallic complex [Ru(bpy)2(tpphz)Zn]4+. The emission intensity of complex decreased as increasing the amounts of Zn2+and the luminescence was almost lost at the ratio of / of 1. After binding to DNA, the peripheral coordination site on the tpphz ligand remained accessible for Zn2+, the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)2tpphz]2+and the nonluminescent heterobimetallic complex was formed. On the other hand, the [Ru(bpy)2(tpphz)Zn]4+also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)2tpphz]2+between the base pairs of DNA. The complex looked like a molecular nut (the Zn2+) and bolt (the [Ru(bpy)2tpphz]2+).

镍(Ⅱ)多吡啶配合物的合成及其插入配体的形状对键合DNA的影响

合成了 2个多吡啶过渡金属镍 (Ⅱ )配合物 [Ni(phen) 2 IP]2 + 和 [Ni(phen) 2 PIP]2 + ,利用质谱和元素分析对配合物进行了表征。利用电子吸收光谱、荧光光谱以及黏度测定研究了配合物与小牛胸腺DNA的作用机制。结果表明 ,配合物与DNA能够以插入模式作用 ,并且由于配合物中的插入配体IP和PIP的形状不同 ,从而使配合物与DNA的键合强弱不同。

联吡啶钌(Ⅱ)配合物的合成、晶体结构及其在染料敏化太阳能电池中的应用

制备了一个多吡啶钌(Ⅱ)配合物[Ru(bipy)2(Pyap)](PF6)2(1)(bipy=2,2′-联吡啶,Pyap=4-(2-吡啶亚甲氨基)-苯酚),研究了它在染料敏化太阳能电池中的应用,对它进行了元素分析、IR、1HNMR、UV-Vis、PL、XRD、CV、IV等表征。将配合物1的水溶液自然蒸发,得到配合物[Ru(bipy)2(Pyap)](PF6)2·H2O(2)的晶体,我们测定了它的单晶结构,配合物2的晶体属单斜晶系,P21/c空间群。配合物1的乙腈溶液在410～490nm处有较宽的对应于MLCT跃迁的紫外吸收峰。在波长为400nm光的激发下,分别在436、463、490nm处各出现了1个荧光发射峰。其CV曲线表明1有2对可逆的氧化还原峰,在-0.158V处有1个不可逆的氧化峰。用配合物1作为光敏染料组装成电池,测得最大输出功率Pmax为0.025mW,短路电流Isc为0.142mA,开路电压Voc为402mV,填充因子ff为0.444,光电转化效率η为0.025%。

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。

Co(phen)_2TATP^(3+)与DNA在旋转金盘金环电极上的相互作用研究

在pH =7.2的Tris缓冲溶液中 ,利用旋转环盘电极法研究了金电极上Co(phen) 2 TATP3 + 与DNA的相互作用 ,并根据扩散控制和电化学控制下得到的各种参数 ,对它们作用的模式进行了讨论 .发现当一定量的DNA存在时 ,Co(phen) 2 TATP3 + 的扩散系数、还原反应的传递系数和半波电位下的速率常数、还原产物Co(phen) 2 TATP2 + 的收集系数和脱出率等都发生了较大幅度的减小 .利用Co(bpy) 3 + 3 进行比较研究表明 ,Co(phen) 2 TATP3 + 与Co(bpy) 3 + 3 在加入DNA后在收集系数和传递系数变化上存在较大的差异 .