钌(Ⅱ)联吡啶配合物cis-[Ru~Ⅱ(bpy)_2(L)_2]的配体取代效应(CNDO/2)

用ＣＮＤＯ／２方法经ＳＣＦ计算获得了钌（Ⅱ）联吡啶配合物ｃｉｓ－［ＲｕⅡ（ｂｐｙ）２（Ｌ）２］的电子结构（其中ｂｐｙ＝２，２′－二联吡啶；Ｌ＝Ｃｌ－，ＮＣＳ－，ＣＮ－，ＮＨ３，ＮＣＣＨ３）．计算结果表明，这些钌（Ⅱ）联吡啶配合物的ＬＵＭＯ均定域于配体ｂｐｙ的最低能π轨道，而其ＨＯＭＯ均定域于中心钌（Ⅱ）原子的ｄπ轨道．随着配体Ｌ的σ电子给予能力的增强，对应配合物的ＨＯＭＯ能级相应增大，ＬＵＭＯ能级亦有所增大，两者之差值则降低．这些钌（Ⅱ）联吡啶配合物的ＨＯＭＯ和ＬＵＭＯ能级变化趋势分别与相应的第一氧化和第一还原电势变化趋势相同，并且ＨＯＭＯ和ＬＵＭＯ能级与其光谱最低吸收能和第一氧化还原电势呈现出很好的线性相关性．计算结果与实验数据相吻合．     

二氰基二硫纶·联吡啶锦(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的合成与表征

以ｃｉｓ－１，２－二氰基乙烯－１，２－二硫醇钠Ｎａ２（ｍｎｔ）和２，２′－联吡啶金属配合物Ｍ（ｂｐｙ）Ｃｌ２为源料，合成了标题配合物Ｍ（ｍｎｔ）（ｂｐｙ），Ｍ＝Ｎｉ（Ⅱ），Ｃｕ（Ⅱ），Ｚｎ（Ⅱ），并经元素分析，热谱，摩尔电导，红外和电子光谱所表征。三者均为四配位的电中性配合物，热分解温度高于３１０℃，可溶于ＤＭＦ，ＤＭＳＯ，吡啶，氯仿和丙酮，难溶于水和乙醚。     

Cu（phen）^2＋3和Cu（bpy）^2＋3与6—巯基嘌呤,腺嘌呤相互作 …

在ｐＨ为７．０的磷酸盐缓冲溶液中，用荧光光谱，紫外光谱，电化学及紫外光谱电化学等方法研究了铜配合物与６－巯基嘌呤，腺嘌呤的相互作用，结果表明，Ｃｕ（ｐｈｅｎ）＾２＋２和Ｃｕ（ｂｐｙ）＾２＋３与６－巯基嘌呤，腺嘌呤发生了相互作用，但作用程度不同，根据荧光光谱实验数据计算出Ｃｕ（ｐｈｅｎ）２＋３和Ｃｕ（ｂｐｙ）＾２＋３与６－巯基嘌呤，腺嘌呤的配位比均为１：１，它们与６－巯基嘌呤作用的配位常数分别为２．     

三核过渡金属配合物[M3^ⅢO（OOCR）6L3]^＋（M=Cr,Fe,Mn;R=CH3,C2H5,CH …

采用＾１Ｈ ＮＭＲ谱研究了通式为（Ｍ３＾ⅢＯ（ＯＯＣＲ）６Ｌ３）＾＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其＾１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁变换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成,表征以…

合成了通式为Ｋ１５Ｈ３〔Ｃｅ（Ｐ２Ｗ１６ＶＯ６１）２〕．６１Ｈ２Ｏ、Ｋ１５Ｈ４〔Ｌｎ（Ｐ２Ｗ１６ＶＯ６１）２〕．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋，Ｐｒ＾３＋，Ｎｄ＾３＋，Ｓｍ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋）的９种镧系元素Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物，并用ＩＲ、ＵＶ、ＮＭＲ、ＥＳＲ、ＸＲＤ、ＴＧ－ＤＴＡ等对其结构和性质进行子研究。该类配合物具有与Ｋ１６〔Ｃｅ（Ｐ２Ｗ１７Ｏ     

碘·(N,N''''联吡啶)·(三苯基膦)合铜(I)的合成和晶体结构

铜（Ｉ）配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义［１］。但由于铜（Ｉ）配合物不稳定,且在多数有机溶剂中的溶解度较小,铜（Ｉ）配合物的合成比较困难。我们在铜（Ｉ）配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜（Ｉ）配合物［ＣｕＸ（ＰＰｈ３）Ｌ］ｎ［２～４］（ｎ＝１,Ｘ＝Ｉ,Ｌ＝１,１０ｐｈｅｎ;ｎ＝２,Ｘ＝Ｂｒ,Ｉ,Ｌ＝Ｃ９Ｈ７Ｎ）,并对它们的结构进行了研究。本文报道一个类似的新配合物［ＣｕＩ（ＰＰｈ３）（ｂｐｙ）］（Ｉ）的合成…     

μ—4,4‘—联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４’－联吡啶为配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ３（４，４＇－ｂｐｙ）３．（ｐｈｅｎ）３］（ＣｌＯ４）６．２Ｈ２Ｏ（１），［Ｃｕ３（４，４＇－ｂｐｙ），（ｂｐｙ）３］（ＣｌＯ４）６．Ｈ２Ｏ（２）和［Ｃｕ３９４，４＇－ｂｐｙ）３．（ＮＯ２－ｐｈｅｎ）３］（ＣｌＯ４）６．６Ｈ２Ｏ（３）。经元素分析，电导，ＩＲ，电子光谱，ＥＳＲ，磁化率等方法进行了表征，推定该配合物具有以４，４’－联吡     

过渡元素Dawson结构的钨钒磷四元杂多配合物的合成与表征

制备了两个系列１２种尚未见文献报道的过渡金属Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物。经元素分析和热重分析确定配合物通式为Ｋ９，１０［Ｐ２Ｍ（Ｈ２Ｏ）Ｗ１５Ｖ２Ｏ６１］．ｘＨ２Ｏ和Ｋ１０，，１１［Ｐ２Ｍ（Ｈ２Ｏ）Ｗ１４Ｖ３Ｏ６１］．ｘＨ２Ｏ）（Ｍ＝Ｆｅ＾３＾＋，Ｃｏ＾３＾＋，Ｎｉ＾２＾＋，Ｍｎ＾２＾＋，Ｃｕ＾２＾＋，Ｚｎ＾２＾＋＿），采用ＩＲ，ＵＶ，ＮＭＲ，ＥＳＲ和ＸＲＤ等方法进行了结构表征。     

Ru（bpy）2（NCS）2染料敏化CdS／Zn^2＋—TiO2复合半导体纳米 …

采用水热法合成了Ｚｎ＾２＋离子掺杂的ＴｉＯ２纳米粒子「Ｚｎ＾２＋掺杂量０．５％（物质的量的比）」,并用光电化学方面研究了经Ｒｕ（ｂｐｙ）２（ＮＣＳ）２（ｂｐｙ＝２,２’－ｂｉｐｙｒｉｄｉｎｅ－４,４’－ｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ）分别敏化的掺杂Ｚｎ＾２＋的ＴｉＯ２电极（简写为Ｚｎ＾２＋ＴｉＯ２）和ＣｄＳ／Ｚｎ＾＋－ＴｉＯ２复合半导体纳米多孔膜电极的光电化学行为。实验证明Ｒｕ（ｂｐｙ）２（Ｎ     

杂多阴离子的有机金属化学(Ⅲ)──缺位Keggin阴离子PW_9O_(34)~(9-)的酯基锡杂多配合物的合成及性质

利用酯基锡与缺位Ｋｅｇｇｉｎ结构杂多阴离子ＰＷ９Ｏ９－３４反应，合成了６种新的杂多阴离子有机金属配合物Ｍ９［（Ｒ′ＯＯＣＣＨＲ″ＣＨ２ＳｎＯＨ２）３（ＰＷ９Ｏ３４）２］·ｘＨ２Ｏ（Ｍ＝（ＣＨ３）４Ｎ＋，Ｋ＋；Ｒ′＝ＣＨ３＿，ＣＨ３ＣＨ２＿；Ｒ″＝Ｈ，ＣＨ３＿），通过元素分析、ＩＲ光谱、紫外电子光谱、１ＨＮＭＲ、３１ＰＮＭＰ、１８３ＷＮＭＲ和ＴＧＡ－ＤＳＣ热分析等测试手段对标题配合物进行了表征和性质研究，确定该系列配合物为Ａ－β－ＰＷ９型夹心配合物结构．     

M(bpy)_3~(2 )(M=Fe,Ru,Os)电子结构与相关性质

报导了对配合物M(bpy)2 M=Fe,Ru,Os)的量子化学密度泛函(DFT)法研究的结果.在B3LYP/LanL2DZ方法与基组的水平上进行计算 ,探讨M(bpy)32 的电子结构特征及相关性质 ,特别是中心原子对配合物的配位键长、光谱性质、电荷布居及化学稳定性等的影响规律 ,为该类配合物的合成 ,为分析光、电、催化作用机理提供理论参考.     

Highlights of the spectroscopy, photochemistry and electrochemistry of [M(CO)4(α-diimine)] complexes, M=Cr, Mo, W

Tetracarbonyl-diimine complexes [M(CO)₄(α-diimine)] (M=Cr, Mo, W; α-diimine=polypyridyl (bpy, phen), pyridine-2-carbaldehyde (R-PyCa) or 1,4-diaza-butadiene, (R-DAB)) have very interesting structural, spectroscopic, electrochemical and photochemical properties. Their comprehensive experimental and theoretical investigations have important implications for our understanding of the chemistry of organometallic complexes with noninnocent ligands. The most interesting physical and chemical aspects of [M(CO)₄(α-diimine)] complexes, which have more general relevance, are highlighted and discussed.     

Increasing the ordering temperatures in oxalate-based 3D chiral magnets: the series [Ir(ppy)2(bpy)][M(II)M(III)(ox)3] x 0.5 H2O (M(II)M(III) = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine; ox = oxalate dianion)

The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [M(II)M(III)(ox)3]- network are reported. The compounds can be formulated as [Ir(ppy)2(bpy)][M(II)Cr(III)(ox)3] x 0.5 H2O (M(II) = Ni, Mn, Co, Fe, and Zn) and [Ir(ppy)2(bpy)]-[M(II)Fe(III)(ox)3] x 0.5 H2O (M(II) = Fe, Mn) and crystallize in the chiral cubic space group P4(1)32 or P4(3)32. They show the well-known 3D chiral structure formed by M(II) and M(III) ions connected through oxalate anions with [Ir(ppy)2(bpy)]+ cations and water molecules in the holes left by the oxalate network. The M(II)Cr(III) compounds behave as soft ferromagnets with ordering temperatures up to 13 K, while the Mn(II)Fe(III) and Fe(II)Fe(III) compounds behave as a weak ferromagnet and a ferrimagnet, respectively, with ordering temperatures of 31 and 28 K. These values represent the highest ordering temperatures so far reported in the family of 3D chiral magnets based on bimetallic oxalate complexes.     

二茂铁基多核配合物的合成及猝灭Ru(bpy)32+发光过程研究

合成了Co²⁺、Ni²⁺、Cu²⁺、Cd²⁺、Zn²⁺等金属的Schiff碱型二茂铁基多核配合物,并对其进行元素分析和光谱表征,发现该类配合物能有效地猝灭Ru(bpy)₃²⁺发光。Stern-Volmer作图呈线性关系并得猝灭速率常数k_q为10⁹L·mol^-1·s^-1数量级,且lgk_a与配合物的氧化还原电位有较好的线性关系;猝灭过程按电子转移机理进行。     

Synthesis, structural characterization, and photophysical, electrochemical, intercomponent energy-transfer, and anion-sensing studies of imidazole 4,5-bis(benzimidazole)-bridged Os(II)Os(II) and Ru(II)Os(II) bipyridine complexes

Homo- and heterobimetallic complexes of composition [(bpy)(2)M(II)(H(2)Imbzim)M'(II)(bpy)(2)](ClO(4))(3)·nH(2)O, where M(II) = M'(II) = Os (1), M(II) = Ru and M'(II) = Os (2), H(3)Imbzim = 4,5-bis(benzimidazole-2-yl)imidazole, and bpy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. Both of the complexes crystallized in monoclinic form with the space group P2(1)/m for 1 and P2(1)/n for 2. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. The complexes display very intense, ligand-centered absorption bands in the UV region and moderately intense metal-to-ligand charge-transfer (MLCT) bands in the visible region. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations. The strong fluorescence of free H(3)Imbzim is completely quenched in the metal complexes by energy transfer to the metal-based units, which exhibit their characteristic MLCT phosphorescence. The luminescence data of the heterometallic complex 2 show that electronic energy transfer takes place from the ruthenium center to the osmium-based component. The anion binding properties of the complexes have been studied in solutions using absorption, emission, and (1)H NMR spectral measurements. The metalloreceptors act as sensors for F(-) and AcO(-) ions. Sensing studies indicate the presence of two successive anion-induced deprotonation steps, leading to the formation of [(bpy)(2)M(HImbzim)M'(bpy)(2)](2+) and [(bpy)(2)M(Imbzim)M'(bpy)(2)](+) species. Double deprotonation is also observed in the presence of hydroxide. The binding affinities of different anions toward the receptors have been evaluated. Cyclic voltammetry measurements carried out in acetonitrile have provided evidence in favor of anion-dependent electrochemical responses of the bimetallic metalloreceptors with F(-) and AcO(-) ions.     

Theoretical Studies on the Fe-M Interactions and 31P NMR in Fe(CO)3(EtPhPpy)2MX2 (X=NCS,SCN, Cl; M=Zn,Cd, Hg)

To study the Fe?M interactions and their effects on 31P NMR, the structures of Fe(CO)3(EtPhPpy)2 1,Fe(CO)3(EtPhPpy)2M(NCS)2 (2: M=Zn, 3: M=Cd, 4: M=Hg) and Fe(CO)3(EtPhPpy)2CdX2 (5: X=Cl,6: X=SCN) were investigated by density functional theory (DFT) PBE0 method. The stabilities S of complexes follow S(2)>S(3)>S(4) and S(3)≈S(6)>S(5), indicating that 6 is stable and may be synthesized.The complexes with thiocyanate are more stable than that with chloride in Fe(CO)3(EtPhPpy)2CdX2.The strength I of Fe-M interactions follows I(2)≈I(3)相似文献   

The circular dichroism of the charge-transfer bands of M(bpy)2+3 (M = Re,Ru, Os)

The absolute configuration of (?)_D-Ru(bpy)₃(ClO₄)₂ has been determined to be the right-hand screw configuration Δ. CD spectra of M(bpy)²⁺₃ (M = Fe, Ru, Os) doped in a uniaxial host. Lattice lead to a new assignment of CD bands in the MLCT region. The CD arises from intrinsically allowed electronic and magnetic transition dipole moments, the latter coming from metal-centered transitions.     

Effects of electron withdrawing and donating groups on the efficiency of tris(2,2'-bipyridyl)ruthenium(II)/tri-n-propylamine electrochemiluminescence

The effects of electron withdrawing and electron donating groups on the electrochemiluminescent (ECL) properties of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+) where bpy = 2,2'-pyridine) are reported. The electrochemistry, photophysics and ECL of (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ (DC = 4,4'-dicarboxy-2,2'-bipyridine; DM = 4,4'-dimethyl-2,2'-bipyridine) have been studied relative to Ru(bpy)3(2+) in 50:50 (v/v) acetonitrile(CH3CN):H2O (0.1 M KH2PO4), and aqueous solutions. Furthermore, the effects of Triton X-100 (polyethylene glycol tert-octylphenyl ether) on the electrochemical, spectroscopic and ECL properties of these compounds are reported. The anodic oxidation of Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ produces ECL in the presence of tri-n-propylamine (TPrA) in all solvent systems. ECL efficiencies (phi(ecl), photons produced per redox event) of 0.73 and 0.84 for (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ were obtained in aqueous buffered solution, using Ru(bpy)3(2+) as a relative standard (phi(ecl) = 1.0). Addition of 0.4 mM Triton X-100 results in a greater than 2-fold increase in ECL efficiences (i.e., 3.8, 2.4 and 2.3 for Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+, respectively) using aqueous Ru(bpy)3(2+) containing no surfactant as standard (phi(ecl) = 1.0). ECL efficiencies of 27.4, 16.5 and 26.1 were found in 50:50 (v/v) CH3CN:H2O (0.1 M KH2PO4) for Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+, respectively, using aqueous Ru(bpy)3(2+) containing no surfactant as standard (phi(ecl) = 1.0). Detailed studies support adsorption of surfactant on the electrode surface, thus facilitating TPrA and ruthenium oxidation.     

Synthesis, luminescence, and electrochemical studies of tris(homoleptic) ruthenium(II) and osmium(II) complexes of 6'-tolyl-2,2':4',2'-terpyridine

The synthesis and photophysical and electrochemical properties of tris(homoleptic) complexes [Ru(tpbpy)3](PF6)2 (1) and [Os(tpbpy)3](PF6)2 (2) (tpbpy = 6'-tolyl-2,2':4',2' '-terpyridine) are reported. The ligand tpbpy is formed as the side product during the synthesis of 4'-tolyl-2,2':6',2' '-terpyridine (ttpy) and characterized by single-crystal X-ray diffraction: monoclinic, P21/c. The tridentate tpbpy coordinates as a bidentate ligand. The complexes 1 and 2 exhibit two intense absorption bands in the UV region (200-350 nm) assignable to the ligand-centered (1LC) pi-pi* transitions. The ruthenium(II) complex exhibits a broad absorption band at 470 nm while the osmium(II) complex exhibits an intense absorption band at 485 nm and a weak band at 659 nm assignable to the MLCT (dpi-pi*) transitions. A red shifting of the dpi-pi* MLCT transition is observed on going from the Ru(II) to the Os(II) complex as expected from the high-lying dpi Os orbitals. These complexes exhibit ligand-sensitized emission at 732 and 736 nm, respectively, upon light excitation onto their MLCT band through excitation of higher energy LC bands at room temperature. The MLCT transitions and the emission maxima of 1 and 2 are substantially red-shifted compared to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2. The emission of both the complexes in the presence of acid is completely quenched indicating that the emission is not due to the protonation of the coordinated ligands. Our results indicate the occurrence of intramolecular energy transfer from the ligand to the metal center. Both the complexes undergo quasi-reversible metal-centered oxidation, and the E1/2 values for the M(II)/M(III) redox couples (0.94 and 0.50 V versus Ag/Ag+ for 1 and 2, respectively) are cathodically shifted with respect to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2 (E1/2 = 1.28 and 1.09 V versus Ag/Ag+, respectively). The tris(homoleptic) Ru(II) and Os(II) complexes 1 and 2 could be used to construct polynuclear complexes by using the modular synthetic approach in coordination compounds by exploiting the coordinating ability of the pyridine substituent. Furthermore, these complexes offer the possibility of studying the influence of electron-withdrawing and electron-donating substituents on the photophysical properties of Ru(II) and Os(II) polypyridine complexes.     

Synthesis, characterization, DNA binding and cytotoxic studies of platinum(II) and palladium(II) complexes of the 2,2'-bipyridine and an anion of 1,1-cyclobutanedicarboxylic acid.

Two neutral complexes of formula [M(bpy)(cbdca)] [where M is palladium(II) (Pd(II)) or platinum(II) (Pt(II)), bpy is 2,2'-bipyridine and cbdca is anion of 1,1-cyclobutanedicarboxylic acid] have been synthesized. These water soluble complexes have been characterized by chemical analysis and conductivity measurements as well as 1H-NMR, ultraviolet-visible and infrared spectroscopy. In these complexes the ligand cbdca coordinates to Pt(II) or Pd(II) as bidentate with two oxygen atoms. They are nonelectrolyte in conductivity water. These complexes inhibit the growth of P388 lymphocytic leukemia cells and their targets are DNA. They invariably show ID50 values less than cisplatin. [Pt(bpy)(cbdca)] and [Pd(bpy)(cbdca)] have been interacted with calf thymus DNA and bind to DNA through coordinate covalent bond. In addition, the influence of binding of these complexes on the intensity of EtBr-DNA have been studied. They bind to DNA via a nonintercalating mode.