无机化学综合实验:Cu(Ⅰ)配合物的合成与光致发光性能

Cu(Ⅰ)配合物的合成与光致发光性能实验是结合无机化学中的配合物基础知识和前沿研究热点设计的综合性实验,包括配合物的制备和光致发光性质表征.本实验中分别制备了立方烷、阶梯状、二聚体等不同结构和不同配体的Cu(Ⅰ)配合物,深入研究了光致发光性能与配合物结构之间的关系.该实验共需12学时完成,实验过程包括配合物制备、减压过滤、荧光光谱测试与分析等,涉及沉淀溶解、配位等多种反应类型和分子光物理性质探究.该综合性实验对实验设备要求低,实验现象明显,产率高,教学过程可操作性强,综合性强.教学实践表明,该实验能显著激发学生学习兴趣,不仅可以让学生加深对无机化学基础知识的理解,还可以获取前沿知识,对提高学生的综合实验能力,培养创新型、复合型人才具有重要意义.     

甲壳胺与Cu(Ⅱ)配合物的合成与表征

在均相条件下 ,通过甲壳胺 (CTS)与CuSO4 反应合成了甲壳胺 Cu(Ⅱ )配合物 ,并用元素分析、IR、X 衍射和TGA对Cu(Ⅱ )与甲壳胺形成的配合物进行了结构表征 .不同pH值下形成的配合物有不同的构型 .在pH =7时配合物是由 1个Cu(Ⅱ )与 1个甲壳胺单元中C2 和C3 位上的—NH2 和—OH进行配合并通过羟基形成了桥式配位结构 .     

Cu(Ⅱ)-atza配合物合成与表征——推荐一个综合化学实验

介绍了Hatza配体的合成方法及在水溶液中合成Cu（Ⅱ）-atza配合物单晶的实验方法与表征手段。该实验反映了科学研究的新成果,知识要点多、学科覆盖面宽、可操作性强、实验效果好,有利于培养学生的实践能力和创新能力。     

Cu(Ⅱ)Fe(Ⅲ)Cu(Ⅱ)异三核配合物的合成及表征

合成了三种以草酸根为桥联配体的异三核配合物。经元素分析、红外光谱、电子光谱、摩尔电导及室温磁矩对配合物的组成和结构进行了表征。研究表明 ,在Cu(Ⅱ ) Fe(Ⅲ ) Cu(Ⅱ )离子间存在着反铁磁相互作用。     

系列Cu(II/I)配聚物的合成、结构及光电性能

采用水热方法合成了3种Cu(II/I)配聚物及超分子,(1)[K2Cu2(ox)(btec)(MeOH)2]n,(2){[Cu(pdc)(H2O)2]· H2O}n,(3)[Cu(cyan)(phen)]·H2O (H2ox:草酸, H4btec:均苯四甲酸, MeOH:甲醇, H2pdc:2,5-吡啶二羧酸, phen:邻菲啰啉, Hcyan:氰尿酸).通过X射线单晶衍射、表面光电压光谱(SPS)、固体紫外-可见(UV-Vis)、傅里叶变换红外(FTIR)光谱、元素分析等方法对配合物进行了表征.结构解析结果表明,配合物(1)是具有三维(3D)无限结构的配聚物;(2)是具有二维(2D)无限结构的配聚物,但又通过氢键进一步连成了三维(3D)网络,(1)与(2)的中心金属均为Cu(II)离子;(3)为含Cu(I)的单核配合物,但又通过氢键和π-π堆积作用,使它成为2D超分子化合物.配合物SPS结果显示,配合物(1)-(3)在300-800 nm范围内都呈现光伏响应,表明三者均具有一定的光电转换能力.讨论了配合物的组成、结构、维数、配体种类、中心金属离子价态及配位微环境对SPS的影响,并将SPS与UV-Vis光谱进行了关联.     

双核Cu(I)配合物的热分解非等温动力学

Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2•1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2•H2O(2), [Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2•H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively. The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt=A•exp(-E/RT) •(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A•exp(-E/RT)• (1-α)2, which corresponds to the mechanism of "the second-order chemical reaction".     

两个基于双咪唑基配体的Co(Ⅱ)/Cu(Ⅰ)配合物的合成、晶体结构及荧光性质

以Co(ClO4)2·6H2O/Cu(ClO4)2·6H2O、1,4-双(咪唑基-1-基)丁烷(bib)/1,4-双(咪唑基-1-基)苯(bix)和4,4-(1,3-苯基双(亚甲基氧基))二苯甲酸(H2pmda)为原料,在水热条件下反应,得到了2个配合物{[Co(bib)3](ClO4)2}n(1)和{[Cu3(bix)(4.5)](ClO4)3}n(2)(H2pmda未参与反应),对它们进行了元素分析、红外光谱、荧光光谱、单晶和粉末X射线衍射表征。配合物1属于三方晶系,R 空间群,a=b=1.39337(5)nm,c=1.74054(13)nm,V=2.9265(3)nm^3,Mr=828.59,Dc=1.410g·cm^-3,F(000)=1293,μ=0.639mm^-1,Z=3,R1=0.0611,wR2=0.1937(I>(2σ(I))。配合物2也属于三方晶系,P 空间群,a=b=2.33441(15)nm,c=0.71511(9)nm,V=3.3749(5)nm^3,Mr=1561.28,Dc=1.536g·cm^-3,F(000)=1602,μ=1.131mm^-1,Z=2,R1=0.0439,wR2=0.1090(I>(2σ(I))。单晶结构分析表明配合物1为含有36元环的二维网状结构,配合物2为含有84元环的二维网状结构,并通过氢键或π-π堆积使它们扩展成超分子结构。此外,还研究了2个配合物的荧光性质。     

含混合配体双核铜(I)配合物的合成与荧光光谱

合成了含双二苯基膦甲烷(dppm)和邻菲咯啉(phen)混合配体的双核铜(I)配合物[Cu(dppm)(phen)]2(NO3)2 1,并经X射线单晶结构分析表征了配合物的结构,研究了配合物的荧光光谱特征,配合物1的结构分析表明,dppm作为桥式双齿配体、phen作为双齿配体分别与铜原子形成四面体配位结构,硝酸根离子位于配合物外界.     

二维网状银(I)配合物的合成及结构表征

用1,10-二(邻氨基苯氧基)癸烷和AgNO3,进行配位反应得到了配合物[Ag2(L)(NO3)2]η(1).并用元素分析,FT-IR和X-射线单晶衍射进行了表征.结果表明,配合物属于单斜晶系,P21/c空间群,晶胞参数为:a=0.5649(l)nm,b=3.3426(7)nm,c=0.9375 (2) nm,β=99...     

配合物EuxM1-x(TTA)3(H2O)2(M=La,Gd)光致发光特性

合成了一系列组成为EuxM1－x(TTA)3(H2O)2(M=La,Gd)的固体配合物,利用红外光谱和荧光光谱研究了配合物结构和发光性质随Eu3＋浓度的变化规律.红外光谱的结果表明,配合物的成份为Eu(TTA)3(H2O)2和M(TTA)3(H2O)2,没有新化合物生成.而荧光光谱的结果显示配合物的发光强度与Eu3＋浓度不成线性关系,其中不发光的M(TTA)3组分对发光有增益作用.对其可能的发光机制进行了探讨.     

Copper(I) Complexes of Bithiazoles

Several new copper(I) complexes of a group of bidentate bithiazole ligands have been isolated. The compounds prepared are bis(2,2′-dimethyl-4,4′-bithiazole)copper(I) perchlorate ([Cu(me-b)₂]ClO₄), bis(4,4′-dimethyl-2,2′-bithiazole)copper(I) perchlorate ([Cu(me-i)₂]ClO₄), bis(2,2′-diphenyl-4,4′-bithiazole) copper(I) perchlorate ([Cu(ph-b)₂]ClO₄), bis(4,4′-diphenyl-2,2′-bithiazole)copper(I) perchlorate ([Cu(ph-i)₂]ClO₄), bis(4,4′,5,5′-tetraphenyl-2,2′-bithiazole)-copper(I) perchlorate ([Cu(ph₄-i)₂]ClO₄, bis(2,2′-bithiazole)copper(l) perchlorate ([Cu(i)₂]CIO₄), 2,2′-bithiazolecopper(I) perchlorate ([Cu(i)ClO₄), (2,2′-bithiazole)bis(triphenylphosphinesulfide)copper(I) perchlorate ([Cu(i)(SPph₃)₂]ClO₄,(2,2′-bithiazole)bis-( triphenylphosphine)copper(I) perchlorate ([Cu(i)(Pph₃)₂]ClO₄), and (4,4′-bithiazole)bis(triphenylphosphine) copper(I) perchlorate ([Cu(b)(Pph₃)₂]ClO₄). Several synthetic techniques were required including one developed in this work which involved the conversion of [Cu(Pph₃)₄]ClO₄ into the thiophosphine complex by reaction with sulfur and subsequent use of this as a labile precursor complex. Optical spectra of the complexes indicate extensive solution dissociation. Several of the complexes ([Cu(ph-b)₂]ClO₄, [Cu(ph-i)₂]CIO₄, and [Cu(i)(Pph₃]ClO₄) were photoluminescent in the solid; one ([Cu(ph-b)₂]ClO₄) showed extensive loss of emission during irradiation. Most of the complexes prepared here appear to bind through the thiazole nitrogen atoms. However, infrared evidence suggests that in two of the complexes thiazole sulfur atoms participate in the bonding.     

Mononuclear Copper(I) 3-(2-pyridyl)pyrazole Complexes: The Crucial Role of Phosphine on Photoluminescence

A series of emissive Cu(I) cationic complexes with 3-(2-pyridyl)-5-phenyl-pyrazole and various phosphines: dppbz (1), Xantphos (2), DPEPhos (3), PPh₃ (4), and BINAP (5) were designed and characterized. Complexes obtained exhibit bright yellow-green emission (ca. 520–650 nm) in the solid state with a wide range of QYs (1–78%) and lifetimes (19–119 µs) at 298 K. The photoluminescence efficiency dramatically depends on the phosphine ligand type. The theoretical calculations of buried volumes and excited states explained the emission behavior for 1–5 as well as their lifetimes. The bulky and rigid phosphines promote emission efficiency through the stabilization of singlet and triplet excited states.     

Synthesis,Structure, and Photophysical Properties of Yellow-Green and Blue Photoluminescent Dinuclear and Octanuclear Copper(I) Iodide Complexes with a Disilanylene-Bridged Bispyridine Ligand

The synthesis, structural, and photophysical investigations of CuI complexes with a disilanylene-bridged bispyridine ligand 1 are herein presented. Dinuclear (2) and ladder-like (3) octanuclear copper(I) complexes were straightforwardly prepared by exactly controlling the ratio of CuI/ligand 1. Single-crystal X-ray analysis confirmed that dinuclear complex 2 had no apparent π…π stacking whereas octanuclear complex 3 had π…π stacking in the crystal packing. In the solid state, the complexes display yellow-green (λ_em = 519 nm, Φ = 0.60, τ = 11 µs, 2) and blue (λ_em = 478 nm, Φ = 0.04, τ = 2.6 µs, 3) phosphorescence, respectively. The density functional theory calculations validate the differences in their optical properties. The difference in the luminescence efficiency between 2 and 3 is attributed to the presence of π…π stacking and the different luminescence processes.     

A Two-coordinate Copper(I) Complex Constructed from Cyanuric acid and 4,4′-bipyridyl: Synthesis, Structure and Photoluminescence

A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.     

Synthesis and Coordination of Tripodal-Containing Copper(I) Complexes

Reaction of copper(I) chloride with 2,2-bis(diphenylphosphinomethyl)-l-phenylthiopropane P₂S produced a dimeric species [(P₂S)CuC1]₂ (2). Treatment of 2 with silver nitrate in acetonitrile gave a hexameric crystalline metal complex {[(P₂S)Cu(CH₃CN)]₆⁺6NO₃} (4), which had a “cyclodextrin-type” structure. A linear polymeric copper complex [(P₂S)Cu(NO₃)]_n was obtained by recrystallization of 4 in chloroform. These complexes were characterized by single crystal analyses, and their coordination behaviors in solution are discussed.     

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…     

Synthesis, Characterization, Spectroscopic and Electro-chemical Properties of New Mono- and Binuclear Copper(I) Complexes with Substituted 2,2''''-Bipyridine

Introduction Copper(I) complexes have received much attention for their being less expensive and environmentally friendly, various coordination geometry, rich photo-chemical and photophysical properties.1-7 It is well known that copper complexes with diimine (2,2'-bipy- ridine, 1,10-phenanthroline and their substituted deriva-tives designated as diimine) generally exhibit low en-ergy metal-to-ligand charge-transfer (MLCT) states lo-cated in the regions of 350650 nm (e ≈ 103—104 dm3昺ol-1昪…     

Synthesis and Supramolecular Structure of Chloro（1,10-phenanthroline ）copper（I） Hexahydrate

1INTRODUCTION Atom transfer radical addition is an efficient me-thod for carbon-carbon bond formation in organic synthesis[1,2].In some of these reactions,a transi-tion-metal catalyst acts as a carrier of the halogen atom in a reversible redox process.The transition-metal-catalyzed has been successfully used to con-trol radical polymerization[3].In the process,the transition-metal species initially abstracts halogen atom X from organic halide to form oxidized species and carbon-centered r…     

Synthesis, Structure and Magnetic Properties of Two New Homotrinuclear Bis(oxamato) Copper(II) Complexes

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Synthesis and Physico-Chemical Properties of Homoleptic Copper(I) Complexes with Asymmetric Ligands as a DSSC Dye

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high V_OC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).