Photo-functional materials based on copper(I) complexes

Nowadays,photonshavebeguntoreplaceelectronsasthecarrierofinformation,andphotofunctionalmaterialshaveplayedanimportantroleintheinformationsociety.Becauseoftheirrichphotochemicalandphotophysicalproperties,copper(I)complexeshavebeenprovedtobegoodmaterialsinmanyfields,suchasorganiclightemittingdiodes,opticalsensor,nonlinearoptics,dyesensitizedsolarcellsandsoon.Manyscientists,suchasFord[1,2],Che[3],Yam[4,5]haveachievedprominentresultsinthisfield.Thegoalofthisarticleistooutlinetheprogressandhotspo…     

Photo-functional materials based on copper(Ⅰ) complexes

Copper(Ⅰ) complexes are attractive photo-functional materials due to their rich photochemical and photophysical properties. It has been proved that these new materials have potential application in many fields, such as organic light-emitting diodes, optical sensor, nonlinear optics and dye sensitized solar cells. The goal of this review is to outline the progress in this field. Many aspects, including new ligands, stereochemical control and the construction of supramolecules, design of the excited states, the high-energy emission and low-energy emission, the Cu-Cu bonding interactions and applications, are discussed.     

The self-aggregation of chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes

The self-aggregation of chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes in water-alcohol system and water-alcohol-NaCl system has been studied by circular dichroism (CD),UV-Vis absorption spectra and fluorescence spectra methods.The experiment results indicate that chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes have two different kinds of aggregates in water-alcohol system and water-alcohol-NaCl system.And the porphyrins may form highly organized and orientated aggregates in water-alcohol-NaCl system.The aggregates in water-alcohol-NaCl system may have helical structures.     

Synthesis,Structural Characterization,and Electrochemical Properties of Binuclear Copper(Ⅱ) Complexes Containing Tetradentate Schiff Base Ligand

Two binuclear copper(Ⅱ) complexes, [Cu2(saloph)2 (μ-O)2]-2(DMF)[H2saloph=N,N′-o-phenylenebis(salicylideneaminato)] (a) and [Cu2(salen)2(μ-O)2] [H2salen=N,N′-bis(salicylic-deneaminato) ethylene] (b)were synthesized and characterized by X-ray crystallography. Both of them have distorted rectangular pyramidal geometry around Cu(Ⅱ). The complete series of complexes show bridging phenoxo groups between the copper centers, together with hydroxo-bridges in these complexes. The complexes have also been characterized by elemental analysis, IR, TG-DTA, and electrochemical results.     

Cu(Ⅰ)配合物型光功能材料研究进展

光功能Cu(Ⅰ)配合物是近年来新材料领域的一个亮点,在有机发光二极管(OLED)、光学传感器、非线性光学材料(NLO)、染料敏化太阳能电池等领域表现出诱人的应用前景. 文中评述了这类材料在配体、立体化学控制和超分子构筑、激发态设计、高能发射(HE)和低能发射(LE)、Cu…Cu间相互作用、应用开发等方面的研究进展.     

Syntheses, characterization, crystal structure and magnetic properties of copper(Ⅱ)α, β-unsaturated carboxylate complexes with trimethyl phosphate

Two ternary complexes Cu2A4[OP(OCH₃)₃]₂ (A represents CH₂== CH—COO- and CH₂== C(CH₃)—COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu₂[CH₂== C(CH₃)—COO]₄[OP(OCH₃)₃]₂ is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α = 91.263(14)°, β = 102.559(6)°, γ = 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four a -methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist antiferromagnetic interactions between the two copper(Ⅱ) atoms.     

六边形纳米CuⅠ电化学传感Cd(Ⅱ)

基于纳米材料的优异特性,根据文献采用一步液相反应法,制备了六边形纳米CuⅠ.并将其制成碳糊电极,采用经典的三电极系统:CuⅠ修饰的碳糊电极为工作电极,饱和KCl的Ag/AgCl电极为参比电极,铂片为对电极,在不同浓度的Cd2+溶液中,用电化学交流阻抗方法研究了其对Cd2+的电化学行为,实验结果表明电荷传递电阻Ret随着Cd2+浓度的增加而减小,实现了CuⅠ对Cd2+的电化学传感.该分析方法操作简单易行,具有潜在的应用价值,而且这些研究结果拓展了纳米材料修饰电极在电分析化学中的重要意义.     

半胱氨酸基硫醇配体分子侧链结构对其Ag(Ⅰ)配位聚合物的影响

设计合成了硫醇类配体N-乙酰-L-半胱氨酰基苯胺(L-1)、N-乙酰-L-半胱氨酰基苯酚酯(L-2)和N-乙酰-L-半胱氨酰基乙酯(L-3),并采用紫外-可见光谱、荧光光谱、圆二色(CD)光谱、动态光散射(DLS)和扫描电子显微镜(SEM)等方法研究了乙醇中L-1～L-3与Ag⁺配位后的光谱性质和形貌特征.结果表明:L-1和L-3与Ag⁺形成了配位聚合物,观察到与Ag(Ⅰ)-Ag(Ⅰ)相互作用相关的吸收和荧光光谱信号,但这两个体系的光谱并不相同;而L-2则与Ag⁺形成了配位寡聚物,其对应的吸收和荧光光谱信号均较弱且峰波长较短.Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-3配位聚合物体系中还观察到对应吸收的CD信号,意味着手性氨基酸残基的分子手性已传递至超分子聚合物中与Ag(Ⅰ)-Ag(Ⅰ)相互作用相关的生色团上,这归因于配体侧链间的相互作用;而Ag(Ⅰ)-L-2配位寡聚物体系则无CD信号.据此推测,Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-3配位聚合物中配体侧链间的相互作用可能是氢键作用,且二者的作用模式并不相同.     

六边形纳米CuⅠ电化学传感Cd(Ⅱ)

基于纳米材料的优异特性,根据文献采用一步液相反应法,制备了六边形纳米CuⅠ.并将其制成碳糊电极,采用经典的三电极系统:CuⅠ修饰的碳糊电极为工作电极,饱和KCl的Ag/AgCl电极为参比电极,铂片为对电极,在不同浓度的Cd2+溶液中,用电化学交流阻抗方法研究了其对Cd2+的电化学行为,实验结果表明电荷传递电阻Ret随着Cd2+浓度的增加而减小,实现了CuⅠ对Cd2+的电化学传感.该分析方法操作简单易行,具有潜在的应用价值,而且这些研究结果拓展了纳米材料修饰电极在电分析化学中的重要意义.     

双核铜(Ⅰ)-膦配合物:Cu2(u-Cl)2(PPh3)3的合成及固体荧光光谱的研究

文章合成了双核铜(Ⅰ)-膦配合物Cu2(u-Cl)2(PPh3)3,并经过X-射线单晶结构分析表征了配合物的结构,研究了配合物的固体荧光光谱特征.研究表明,配合物的固体荧光光谱性质主要来源干配体PPh3.     

Photoelectrical performance of nanocrystalline TiO_2 film electrode sensitized by Ru(Ⅱ)-bipyridine complexes

Two kinds of Ru(Ⅱ)-bipyridine complexes, cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(Ⅱ) and cis-di(thiocyanate)bis(2,2′-bipyridyl-3,3′-dicarboxylate) ruthenium(Ⅱ), were utilized as the sensitizers to the nanocrystalline TiO-2 film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO-2 film electrodes with TiCl-4 was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO-2 electrodes.     

基于Cu(Ⅰ)配合物的有机电致发光器件研究进展

Cu(Ⅰ)配合物作为一种磷光材料,其内量子效率理论上可达到100%,比荧光材料高出三倍.因其还具有价格低廉、无毒性、储量大、结构多样化、光物理性质独特等特点使其被广泛关注.本文按照发光颜色分类综述了一些常见的Cu(Ⅰ)配合物的电致发光研究进展及其电致发光器件结构,并对基于Cu(Ⅰ)配合物有机电致发光器件研究的前景进行了展望.     

双核Ag(Ⅰ)配合物的合成、结构及光物理研究

采用水热合成法,得到Ag(Ⅰ)的配合物Ag2(Sal)2(Sal=邻羟基苯甲酸).对该配合物的单晶进行了X-射线衍射分析,确定了结构.配合物为单斜晶系,P2(1)/c空间群,a=0.742 8(17) nm,b=0.886(2) nm,c=1.067(3) nm,β=107.92(3)o,V=0.668(3) nm3, Z=2,Dc=2.436 g/cm3,Gof=1.301,R1=0.086 0.对该配合物的UV-VIS-NIR,IR和荧光光谱进行了测定.结果表明该配合物在λex=345 nm条件下,在418～504.5 nm范围内有3个发射峰,可以分别指认为LLCT和LMCT.     

二维蜂窝状配位聚合物Ag(Ⅰ)-3,6-二(2-吡啶巯基)哒嗪的合成(英文)

合成了银(Ⅰ)的3,6-二(2-吡啶巯基)哒嗪配合物,{[Ag2(C14H10N4S2)3]n.4.5nH2O.2nNO3-}(1),通过红外光谱、元素分析和单晶X射线分析技术给予表征。配合物1是具有(6,3)拓扑的二维蜂窝网状结构的配位聚合物,银(I)中心为三角平面配位几何构型。晶体结构为三角晶系,R-3:空间群,a=15.555(3),b=15.555(3),c=42.587(8),α=β=90°,γ=120°,Z=6,V=892 4(3)3,R1=0.064 5,wR2=0.213 3。二维网状结构沿着c轴准确堆积为具有一维通道的(6,3)拓扑蜂窝层。配合物1的循环伏安测定表明电极反应是准可逆反应。     

TiO_2纳米管对Cu(Ⅱ)和Ag(Ⅰ)的吸附和光催化还原作用研究

以纳米TiO2为原料,采用水热合成法制备TiO2纳米管.FT-IR表征表明含有较为丰富的羟基;XRD表征表明TiO2纳米管主要为锐钛矿相,有少量的金红石相;BET比表面积为96.5m2.g-1.TiO2纳米管吸附Cu(Ⅱ)和Ag(Ⅰ)的结果表明,吸附符合朗格缪尔吸附等温线模型,Cu(Ⅱ)和Ag(Ⅰ)的qmon分别为2.41×10-5、13.3×10-5 mol.g-1,K分别为3.95×103、6.35×103 L.mol-1.在300W的紫外灯照射下进行光催化实验,结果表明反应近似符合一级模型,反应级数与金属离子在TiO2纳米管表面的吸附平衡常数相关;TiO2纳米管对Cu(Ⅱ)和Ag(Ⅰ)具有较高的光催化活性.     

新型配体9'-(4,5-二烷基硫-1,3-二硫杂环戊烯-2-叉)4',5'-二氮杂芴的铜(Ⅰ)配合物的合成及光谱研究

首次用Cu(CH3CN)4ClO4与新型配体9'-(4,5-二烷基硫-1,3-二硫杂环戊烯-2-叉)4',5'-二氮杂芴合成了两种Cu(Ⅰ)配合物,并对配合物进行了元素分析和光谱的测定.提出了一维链状的可能结构.     

原位制备磁性壳聚糖纳米粒子及其对Ag(Ⅰ)的吸附性能

以壳聚糖、Fe2+/Fe3+盐为水相,环已烷/正已醇为油相,Triton X-100为乳化剂,通过在W/O微乳体系中加NaOH溶液沉淀剂,原位制备磁性壳聚糖纳米粒子(MCN),用于吸附Ag(Ⅰ).考察了pH值、Ag (1)浓度和温度对MCN吸附Ag(Ⅰ)的影响.结果表明,MCN分散良好,粒径15 ～40 nm,饱和磁化强度25.6 emu·g-1,pH6.0时吸附最佳,Ag(Ⅰ)吸附容量随温度升高而降低.吸附动力学符合拟二级方程,且为自发放热过程.吸附等温线分别用Langmuir,Freundich和D-R模型拟合,表明Langmuir模型拟合最好,为单分子层吸附,最大吸附容量2.06 mmol/g.吸附活化能E为8.94 ～9.10 kJ/mol,表明以化学吸附为主.     

两个新的Schiff碱双核配合物[Zn2(L)2(py)2](1)和[Cu2(L)2(py)2](2)的合成、晶体结构和光谱性质

利用Sehiff碱配体N-(2-羟苄基)水杨醛亚胺(H2L)合成了两个双核配合物[Zn2(L)2(py)2](1)和[Cu2(L)2(py)2](2).单晶X射线衍射结果表明,配合物(1)属单斜晶系,空间群P2(1)/c,a=1.014 5 nm,b=1.380 6 nm,c=1.267 1 nm,β=102.063°,V=1.735 5 nm3,Z=2,F(000)=760,μ=1.43 mm-1,R1=0.036 1,wR2=0.084 0,中心离子采取三角双锥的配位构型;配合物(2)属单斜晶系,空间群P2(1)/n,a=0.821 06 nm,b=1.071 5 am,c=1.786 4 nm,β=99.365°,V=1.550 7 nm3,Z=2,F(000)=756,μ=1.422 mm-1,R1=0.038 6,wR2=0.074 6,中心离子采取四方锥的配位构型.