双核三联吡啶钌（Ⅱ）配合物的合成及其光谱和电化学性质

双核三联吡啶钌（Ⅱ）配合物的合成及其光谱和电化学性质;三联吡啶;双核钌（Ⅱ）配合物;光谱法;电化学性质     

三联吡啶铁配位聚合物电致变色材料的合成及性能

将芳环作为桥联基团引入到2个三联吡啶单元之间构建多齿配体,与四氟硼酸亚铁六水合物配位,制备了一类新型的三联吡啶铁配位聚合物,并研究了其在水系电解液中的电致变色性能。研究结果表明,芳环上氟原子的引入对材料电致变色性能具有一定的影响。其中,采用含有2个氟原子的配体F2制备的铁配位聚合物Fe-F2表现出优异的电致变色性能（光学对比度高达69%,响应时间短至0.5 s,着色效率超过320 cm²·C^-1）。     

三联吡啶铁配位聚合物电致变色材料的合成及性能

将芳环作为桥联基团引入到2个三联吡啶单元之间构建多齿配体，与四氟硼酸亚铁六水合物配位，制备了一类新型的三联吡啶铁配位聚合物，并研究了其在水系电解液中的电致变色性能。研究结果表明，芳环上氟原子的引入对材料电致变色性能具有一定的影响。其中，采用含有2个氟原子的配体F2制备的铁配位聚合物Fe-F2表现出优异的电致变色性能(光学对比度高达69%，响应时间短至0.5 s，着色效率超过320 cm²·C^-1)。     

溴代酞菁铁配合物的光谱电化学性质研究

本文对μ-氧-四溴酞菁铁配合物([TBPcFe]₂O)的电化学性质及光谱电化学性质进行了研究。结果表明,μ-氧-四溴酞菁铁在所研究的电压区问内经历了三个单电子氧化还原反应,其半波电势为0.06V,—0.75V及—1.33V(相对于甘汞电极),分别对应于Fe³⁺/Fe³⁼、Fe²⁺/Fe⁺及TBPc^2-/TBPc^3-电对的氧化还原反应。光谱电化学性质研究亦观察到相应酞菁配合物的特征光谱。     

苯胺吡啶双铑配合物的氧加合物合成、谱学和电化学研究

苯胺吡啶双铑配合物两种异构体的双氧加合物被合成和鉴定:Rh_2(ap)_4O_2(4,0)为4,0异构体的氧加合物1(ap=2-anilinopyridine 2-苯胺吡啶),Rh_2(ap)_4(2,2)为2,2反式异构的氧加合物2.其ESR谱有超氧离子(O_2~-)的特征信号g=2.03。4,0异构体轴向配体不同时A_n值的次序为:O_2~-≈ClO_4~-相似文献   

含咪唑盐的三联吡啶铜配合物的合成和分子结构

通过带有不同长度的4-(4-氯烷氧基苯基)-2,2':6,2″-三联吡啶和N-甲基咪唑在甲苯中加热反应,制备了3种由烷氧基桥联的新型三联吡啶咪唑配体。研究了配体和过渡金属离子的配位反应。测定了三联吡啶咪唑铜配合物的单晶分子结构,在铜配合物中,Cu(Ⅱ)和两个三联吡啶单元形成扭曲八面体配位方式。Monoclinic,空间群P 21/c;a=1.7229(3) nm,b=1.5924(2) nm,c=2.1590(3) nm,α=90°,β=101.332(2)°,γ=90°,M_r=1298.09,V=5.8078(15) nm³,D_c=1.485 mg/m³,Z=4, F(000)=2684。     

基于二甲基苯并联咪唑的钌(Ⅱ)多吡啶配合物的合成、光谱和电化学性质

合成了一组钌多吡啶化合物[Ru（bpy）₂（DMBbimH_x）]^y+（bpy=2,2''-联吡啶,DMBbimH₂=7,7''-二甲基-2,2''-苯并联咪唑,1-A：x=2;y=2;1-B：x=1,y=1;1-C：x=0,y=0）并测试了它们的核磁氢谱、紫外吸收和电化学性质。随着DMBbimH_x配体逐个脱去质子,配合物的光谱和电化学性质发生明显的变化。有趣的是,脱去一个质子的配合物1-B在不同极性的二氯甲烷和乙腈中的电化学性质呈现明显的差异：在二氯甲烷中,单核的1-B却能发生两步氧化,这是因为在弱极性的溶剂中,[Ru（bpy）₂（DMBbimH）]⁺阳离子通过氢键结合形成二聚体,[Ru（bpy）₂（DMBbimH）]⁺阳离子间存在质子耦合电子传递现象。在1-B的二氯甲烷溶液中得到了化合物[Ru（bpy）₂（DMBbimH）]PF₆·2CH₂Cl₂（2）的单晶。晶体结构分析表明[Ru（bpy）₂（DMBbimH）]⁺阳离子确实通过氢键结合形成二聚体,这与电化学测试的结果一致。而在极性较大的乙腈中,氢键二聚体不能稳定存在,在循环伏安曲线上只有一个峰存在。     

三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究

采用密度泛函理论方法(DFT),对三联吡啶铂(Ⅱ)配合物的结构与电子光谱进行了系统研究.筛选的PBE/LanL2DZ(6-311+G(d))—BMK/LanL2DZ(6-31+G(d))方法,计算结果能较好地与实验值吻合:对光谱峰波长的计算,吸收光谱和发射光谱平均误差分别为14 nm和17 nm.通过对前线分子轨道的分析,归属了各光谱峰的跃迁类型.计算结果表明,不同推拉电子效应的取代基对配合物光谱峰的位置和跃迁类型具有较大影响,为已有的实验结论提供了有力的理论阐述.     

三联吡啶钌复合膜修饰电极电化学发光法测定马来酸氯苯那敏

以氧化铟锡(ITO)导电玻璃为基质,研制了一种SiO2/Ppy/PSS/Ru(bpy)32+复合膜修饰电极。在pH 8.00磷酸盐缓冲溶液中,马来酸氯苯那敏(CM)在修饰电极的电化学发光强度(ECL)有强增敏作用,据此建立了一种灵敏地测定马来酸氯苯那敏的电化学发光的方法。其ECL增加程度与CM的浓度在30～100μmol.L-1之间呈线性关系。方法的检出限(3S/N)为9.0×10-2μmol.L-1。对2.0μmol.L-1马来酸氯苯那敏标准溶液连续测定11次,测定值的相对标准偏差为1.3%。方法用于维C银翘片中马来酸氯苯那敏的测定,回收率在96.5%～98.8%之间。     

新型三联吡啶铜配合物的晶体结构及DNA切割活性

本文合成了新型三联吡啶铜配合物[Cu(ttpy)(acetone)Cl]·(NO₃)(H₂O)₃(ttpy=4′-p-tolyl-2,2′∶6,2″-terpyridine),通过元素分析和X-射线单晶衍射进行结构表征。该配合物属三斜晶系,空间群为P1,晶胞参数为a=0.847 6(3) nm,b=1.265 0(5) nm,c=1.422 7(5) nm,α=111.017(7)°,β=92.174(7)°,γ=90.562(7)°,V=1.422 5(9) nm³,Z=2,D_c=1.309 Mg·m^-3,μ(Mo Kα)=9.00 cm^-1,F(000)=578,R₁=0.063 3,wR=0.141 4。在配合物中,中心铜原子的配位环境为变形四方锥,并通过分子内和分子间的C-H…Cl和C-H…O氢键作用形成三维梯状结构。凝胶电泳结果表明,在pH=7.4,温度37°,以抗坏血酸为还原剂的条件下,该配合物对超螺旋pUC19 DNA表现出一定的切割活性。紫外-可见光谱结果显示,该配合物与四种核苷的反应活性顺序为：5′-GMP>5′-AMP>5′-TMP≈5′-CMP。     

Electrochemistry and Spin-Crossover Behavior of Fluorinated Terpyridine-Based Co(II) and Fe(II) Complexes

Due to their ability to form stable molecular complexes that have tailor-made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding Co^II and Fe^II complexes were synthesized and characterized by single-crystal X-ray structural analysis, electrochemistry and temperature-dependent SQUID magnetometry. Single crystal X-ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin Co^II and Fe^II centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis-NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction.     

Polystyrene with Pendant Mixed Functional Ruthenium(II)‐Terpyridine Complexes

A vinyl substituted 2,2′:6′,2″‐terpyridine and a mixed, bifunctional ruthenium(II)‐terpyridine complex bearing a vinyl and a hydroxymethyl group are utilized as comonomers for radical copolymerization with styrene. The resulting polymers are characterized by means of UV‐vis spectroscopy and gel permeation chromatography, coupled with an in‐line diode array spectrophotometer.     

Synthesis of A New Terpyridine Ligand Combined with Ruthenium(II) Complex and its Usage in the Stepwise Fabrication of Complex Polymer Wires on Gold

Summary: A ruthenium complex-combined terpyridine ligand, tpyRu(dpp)-(epe)- tpyPF₆, was synthesized. Stepwise coordination reactions at the gold surface using this ligand gave Co-Ru hetero-metal complex wires, [ 1Co1Ru ], which underwent reversible redox reactions of both redox complex units.     

Tetrathiafulvalene-Inserted Diphenoquinone: Synthesis,Structure, and Dynamic Redox Property

A new tetrathiafulvalene (TTF) derivative is synthesized, which is substituted with two phenoxy radicals on one 1,3-dithiole ring, and may have either open-shell diradical or closed-shell extended-quinoidal ground states. X-ray single crystal analysis and NMR measurements prove that this molecule has a closed-shell extended quinoidal structure both in the solid state and in solution. DFT calculations show the donor–acceptor electronic properties of this molecule with a well-separated HOMO–LUMO distribution and a small HOMO–LUMO energy gap. Because of this donor–acceptor character, this molecule gives both the dication and the dianion species by electrochemical oxidation and reduction. Furthermore, during the redox process between the neutral and dication states, this molecule exhibits unique changes in the cyclic voltammogram upon repeating the cycles or varying the scan rate. The observed electrochemical behavior is explained by the conformational changes in the electrochemically generated species, thus indicating that this molecule is classified as a dynamic redox system.     

新型吲嗪三联吡啶的合成及其荧光性能

以醋酸钯为催化剂,三环己基膦为配体,碳酸铯为碱,甲苯为溶剂,4-溴-三联吡啶和2-甲酸甲酯-吲嗪经Heck偶联反应合成了一个新型的吲嗪三联吡啶(3),其结构经¹H NMR, ¹³C NMR和HR-MS表征。并研究了3的荧光性能。结果表明：溶剂极性增加,3的荧光强度降低,最大发射波长红移;Cu²⁺可完全淬灭3的荧光;3的Cu²⁺, Cd²⁺, Zn²⁺配合物对部分氨基酸有荧光响应。     

Synthesis and Characterization of Poly(phenylacetylene)s with Ru(II) Bis‐Terpyridine Complexes in the Side‐Chain

An alkyne‐functionalized ruthenium(II) bis‐terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size‐exclusion chromatography (SEC), ¹H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV–vis absorption spectroscopy. In addition, spectro‐electrochemical measurements are carried out. Time‐resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)₂²⁺ model complex.

     

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)

A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.