基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

亚铜配合物的光致发光与电致发光研究

亚铜[Cu（Ⅰ）]配合物因其低廉的价格、多样化的结构和独特的光物理性质一直备受关注.本文综述了常见磷光Cu（Ⅰ）配合物[Cu（NN）2]＋、[Cu（NN）（PP）]＋和（CuX）mLn（其中NN表示双齿二胺配体,PP表示二膦配体,X表示卤素,L表示含N或P配体）的光致发光与电致发光研究,揭示配合物结构与光学性质的关系,探讨近年来Cu（I）配合物在有机发光二极管（OLED）领域的应用研究新进展.     

三核铜（Ⅰ）配合物的合成与结构

三核铜（Ⅰ）配合物的合成与结构杨瑞娜吴生林王冬梅金斗满（河南化学研究所郑州４５０００３）罗保生谌了容（武汉大学分析测试中心４７００５３）含双齿膦配体ｄｐｐｍ（双二苯基膦甲烷）的低氧化态金属配合物由于其特殊的成键性质，反应性和催化性能而日益受到化学专家...     

酰胺型配体铜、锌、银配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了5个配合物[CuLCl₂]·CH₃COCH₃ (1)、[ZnLCl₂]·CH₃COCH₃ (2)、[ZnL(NO₃)₂]·0.5CH₃COCH₃ (3)、[AgL₂]ClO₄ (4)和[AgL₂]BF₄ (5)(L=2-(5-氯-8-喹啉氧基)-1-(吡咯烷-1-基)乙酮)。配合物1和2同构,五配位的中心金属离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个氯离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。配合物4和5中,中心金属与配体的比例为1:2。银离子与2个三齿配位的配体L配位,采取扭曲的八面体配位构型。乙腈溶液中,配合物1、2、4和5在410 nm处的最大荧光发射峰与配体L相似。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

酰胺型配体铜、锌、银配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了5个配合物[CuLCl₂]·CH₃COCH₃（1）、[ZnLCl₂]·CH₃COCH₃（2）、[ZnL（NO₃）₂]·0.5CH₃COCH₃（3）、[AgL₂]ClO₄（4）和[AgL₂]BF₄（5）（L=2-（5-氯-8-喹啉氧基）-1-（吡咯烷-1-基）乙酮）。配合物1和2同构,五配位的中心金属离子采取扭曲的四方锥配位构型,与来自配体L的2个氧原子和1个氮原子及2个氯离子配位。而在配合物3中,锌离子与1个三齿配位的配体L,1个单齿配位的硝酸根和1个双齿配位的硝酸根配位,配位构型为扭曲的八面体。配合物4和5中,中心金属与配体的比例为1∶2。银离子与2个三齿配位的配体L配位,采取扭曲的八面体配位构型。乙腈溶液中,配合物1、2、4和5在410 nm处的最大荧光发射峰与配体L相似。而配合物3由于配体到锌离子之间的能量转移,最大荧光发射峰红移至430 nm。     

含双二苯基膦甲烷双核铜Ⅰ配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷(dppm)的双铜(Ⅰ)配合物[Cu₂(dppm)₂L₂](NO₃)₂(配体L分别是2,2'-联吡啶(1)、邻菲咯啉(2)、2,9-二甲基-邻菲咯啉(3)、吡啶(4)],并经核磁、热分析、光电子能谱等方法表征了配合物的性质。配合物(1)的晶体结构显示,dppm作为桥式双齿配体、联吡啶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。     

双核铜配合物的合成、结构和性质研究

双核铜配合物的合成、结构和性质研究＊杨瑞娜薛宝玉王冬梅侯益民金斗满（河南化学研究所，郑州４５０００３）李彩云（平原大学，新乡４５３００３）关键词铜双核配合物氧化加成中图分类号Ｏ６２７．１２众所周知，许多金属酶具有铜（Ⅰ）、铜（Ⅱ）活性中心，铜配合物具...     

喹啉基对二氧四胺大环铜配合物结构和性质的影响

喹啉基对二氧四胺大环铜配合物结构和性质的影响卜显和，安道利，朱志昂，张智慧，陈荣悌（南开大学化学系，天津３００００７１）二氧四胺大环（ｍａｃｒｏｃｙｃｌｉｃｄｉｏｘｏｔｅｔｍａｍｉｎｅ）配体因其独特的结构特点和功能而受到广泛的重视和关注［１］。通过在...     

Three-Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue-emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three-dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band-edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self-trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non-perovskite bimetallic halide with highly efficient and stable blue light emission.     

NIR-Ⅱ Excitation and NIR-I Emission Based Two-photon Fluorescence Lifetime Microscopic Imaging Using Aggregation-induced Emission Dots

Near-infrared(NIR)lights are powerful tools to conduct deep-tissue imaging since NIR-Ⅰ wavelengths hold less photon absorption and NIR-Ⅱ wavelengths serve low photon scattering in the biological tissues compared with visible lights.Two-photon fluorescence lifetime microscopy(2PFLM)can utilize NIR-Ⅱ excitation and NIR-Ⅰ emission at the same time with the assistance of a well-designed fluorescent agent.Aggregation induced emission(AIE)dyes are famous for unique optical properties and could serve a large two-photon absorption(2PA)cross-section as aggregated dots.Herein,we report two-photon fluorescence lifetime microscopic imaging with NIR-Ⅱ excitation and NIR-Ⅰ emission using a novel deep-red AIE dye.The AIE-gens held a 2PA cross-section as large as 1.61×10⁴GM at 1040 nm.Prepared AIE dots had a two-photon fluorescence peak at 790 nm and a stable lifetime of 2.2 ns under the excitation of 1040 nm femtosecond laser.The brain vessels of a living mouse were vividly reconstructed with the two-photon fluorescence lifetime information obtained by our home-made 2PFLM system.Abundant vessels as small as 3.17μm were still observed with a nice signal-background ratio at the depth of 750μm.Our work will inspire more insight into the improvement of the working wavelength of fluorescent agents and traditional 2PFLM.     

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.     

2-[(二苯基膦基)甲基]吡啶铜(I)配合物的合成及光物理和电致发光性质

合成了3个2-[(二苯基膦基)甲基]吡啶(L)铜(Ⅰ)配合物：Cu(L)2(BF4)(a)、Cu(L)(PPh3)2(BF4)(b)和Cu(L)(POP)(BF4)(c)(POP为双[(2-二苯膦基)苯基]醚),其组成和结构分别经1H NMR、31P NMR、元素分析及晶体结构分析确证。 分子中,中心铜(Ⅰ)离子均为扭曲的四面体配位构型。 在除气的二氯甲烷溶液中,配合物均出现261~274 nm强π-π*吸收,未见明显的Cu→L电荷转移(MLCT)跃迁吸收。 配合物的薄膜样品发射蓝绿光,最大发射峰分别在515、476和481 nm处,光致发光效率分别为16.0%、12.9%和7.0%。 以聚乙烯咔唑(PVK)与配合物b为发光层的多层电致发光器件,当电流密度为1.0×10-3 A/cm2时,电致发光的电流效率为0.36 cd/A,最大亮度为217 cd/m2。     

Three‐Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue‐emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three‐dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band‐edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self‐trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non‐perovskite bimetallic halide with highly efficient and stable blue light emission.     

Sm(DBM)3phen的光致发光和电致发光性质

制备了一系列基于配合物Sm(DBM)3phen的电致发光器件. 研究了其光致发光(PL)和电致发光(EL)性质, 实验结果表明, Sm(DBM)3phen具有良好的电子注入和传输性能以及电致发光性能. 器件ITO/TPD(50 nm)/Sm(DBM)3phen(50 nm)/Alq3(30 nm)/LiF(1.0 nm)/Al的最大亮度和最大效率分别为150 cd/m2和0.72 cd/A, 器件表现为纯Sm3+离子的发光.     

具有聚集诱导发光特性的含氟有机金属配合物的研究进展

近年来,具有聚集诱导发光(aggregation-induced emission,AIE)特性的化合物由于在聚集态或固态发光量子效率较高而受到很多关注.含氟的功能化合物,由于氟原子的存在,往往具有独特的结构和物理、化学及生物学性质.根据中心金属和配体的种类,汇总了具有AIE性质的且含有氟代配体的有机金属配合物的研究进...     

Microwave—enhanced Mannich Condensation of Terminal Alkynes,Primary Amines with Paraformaldehyde on cuprous Iodide Doped Alumina under Solvent Free Conditions

A microwave-enhanced,solventless Mannich condensation of terminal alkynes,primary amines with paraformaldehyde on cuprous iodide doped alumina has been investigated.The structures of products depend on the ratio of alkyne to amine and paraformaldehyde.     

吡唑啉酮类稀土配合物的发光性质研究

合成了一系列吡唑啉酮类稀土铽、铕、钐、钆、镝的配合物, 并采用元素分析、红外光谱和紫外-可见光谱对其进行了表征, 解析了铕配合物的晶体结构. 测定了配体的三重态能级, 研究了这4种配合物的发光性质. 并通过研究配体到稀土离子的能量传递过程, 合理地解释了这些稀土配合物发光性质的差异.     

Crystal Structure and Characterization of a Dye with Two-photon Pumoed Frequency-upconverted Lasing Properties

The title compound, trans-4-[ p-( N-ethyl-N-(hydroxyethyl ) amino) styryl ]-N-methylpyridiniumtetraphenylborate (abbreviated as ESMT, C46H49N4OB) crystallizes in a space group P1- with a= 0. 983 23 (15)nm, b=1.410 73(16) nm, c=1.54 21(12) nm, a=95.252(13)°, β=91.959(17)°, γ= 107.421(12)°, Z=2, F(000)=712, μ= 0.1 mm-1 Mo Ka radiation, R=0. 093 8. The result shows that the cation of themolecule almost lies in one plane, the hydroxyethyl group is perpendicular to the plane, the anion takes a slightdistorted tetrahedral geometry. Also the thermal stability, two-photon fluorescence, two-photon pumped lasingproperty for the title compound were studied.