基于过渡金属配合物的阻变存储材料

阻变型电存储依靠外加电场作用下存储介质的导电性高低差异,即电学双稳态或多稳态来实现数据存取,并具有高容量、高柔韧性、低成本、低能耗、可规模化等优点,为下一代高密度存储技术提供新前景. 除了无机氧化物、碳纳米材料、有机小分子和有机聚合物半导体材料之外,近年来,过渡金属配合物在阻变型电存储方面的应用也引起广泛关注. 本文对迄今为止报道的大部分基于过渡金属配合物的阻变存储材料进行了总结和讨论,主要包括第VⅢ族金属[包括Fe（Ⅱ）、Ru（Ⅱ）、Co（Ⅲ）、Rh（Ⅲ）、Ir（Ⅲ）、Pt（Ⅱ）等配合物]、第IB族和ⅡB族金属[Cu（Ⅱ）、Au（Ⅲ）、Zn（Ⅱ）等配合物]和镧系过渡金属配合物[Eu（Ⅲ）及其它],并对各种配合物的存储行为和存储机理进行了探讨. 过渡金属配合物具有清晰可逆的氧化还原过程,通过改变配体的结构和金属的种类可以很方便地调节材料的前线轨道能级和能隙,利于形成电学双稳态或多稳态,达到二进制或多进制存储的目的,具有潜在应用价值.     

Luminescent Anion Sensing by Transition-Metal Dipyridylbenzene Complexes Incorporated into Acyclic,Macrocyclic and Interlocked Hosts

A series of novel acyclic, macrocyclic and mechanically interlocked luminescent anion sensors have been prepared by incorporation of the isophthalamide motif into dipyridylbenzene to obtain cyclometallated complexes of platinum(II) and ruthenium(II). Both the acyclic and macrocyclic derivatives 7⋅Pt , 7⋅Ru⋅PF₆ , 10⋅Pt and 10⋅Ru⋅PF₆ are effective sensors for a range of halides and oxoanions. The near-infra red emitting ruthenium congeners exhibited an increased binding strength compared to platinum due to the cationic charge and thus additional electrostatic interactions. Intramolecular hydrogen-bonding between the dipyridylbenzene ligand and the amide carbonyls increases the preorganisation of both acyclic and macrocyclic metal derivatives resulting in no discernible macrocyclic effect. Interlocked analogues were also prepared, and preliminary luminescent chloride anion spectrometric titrations with 12⋅Ru⋅(PF₆)₂ demonstrate a marked increase in halide binding affinity due to the complementary chloride binding pocket of the [2]rotaxane. ¹H NMR binding titrations indicate the interlocked dicationic receptor is capable of chloride recognition even in competitive 30 % aqueous mixtures.     

目视法检测阴离子用显色剂的研究进展

评述了以超分子化学分子识别为基础发展起来的新型阴离子目视显色剂,内容主要包括显色剂对选择性阴离子的显色属性以及显色属性和显色剂结构的关系.     

基于纳米多孔薄膜光学干涉的光学传感器

光学传感器是一种利用光把介质与目标分子的相互作用转换为光信号的装置.光学干涉是光学传感器中常用的技术,具有无需标记、无破坏性、响应迅速等优点.在光学传感器中光的干涉主要源于从单层薄膜上下表面反射的光或者从多层薄膜各个界面处反射的光.由于纳米多孔薄膜具有较高的比表面积,将其应用于传感器中能够提高传感器的灵敏度、降低检测限.常见的薄膜类型主要有单层、双层、多层（光子晶体）等.本文综述了多孔硅、阳极氧化铝、二氧化钛、金属有机骨架等纳米多孔薄膜材料的光学干涉在传感器中的应用,并对其进行了展望.     

Gelatinizing of Aqueous Solutions of Transition-Metal Complexes

The gelatinizing of aqueous solutions of transition-metal complexes with hydroxy acids was studied. The mechanism of gelatinizing of these solutions was suggested.     

Photochemical Reactions of Ligands in Transition-Metal Complexes

Three types of photochemical reaction of coordination compounds are well-known and have often been discussed: redox reactions, substitutions, and isomerizations. Less well known is a fourth type of reaction, which occurs fairly frequently: reaction of the ligands themselves. It is the purpose of this article to fill the corresponding gap in the photochemical literature and to summarize our current knowledge of such reactions and of their mechanisms and possible applications.     

Water-Soluble Luminescent Lanthanide Complexes Based on 2-Methacryloyloxyethyleniminodiacetic Acid Copolymers

Doklady Chemistry - 2-Methacryloyloxyethyleniminodiacetic acid and its new water-soluble copolymers with N-vinylpyrrolidone have been synthesized. The interaction of the copolymers in dilute...     

Nonlinear d10-ML2 Transition-Metal Complexes

Invited for this month′s cover is the group of Prof. F. Matthias Bickelhaupt. The cover picture illustrates the authors′ quantum chemical finding that π electrons can significantly bend otherwise linear d¹⁰-ML₂ complexes through backbonding. For more details, see the Full Paper on p. 106 ff.The Group of F. Matthias BickelhauptDepartment of Theoretical Chemistry Amsterdam Center for Multiscale Modeling VU University E-mail: ln.uv@tpuahlekciB.M.FInstitute for Molecules and Materials Radboud University Nijmegen     

New Optical Chemical Sensors Based on Surface Piasmon Resonance

A kind of new optical chemical sensors based on surface plasmon resonance (SPR) have been developed recently in this laboratory. Traditionally, the sensors based on SPR are making use of a coupling prism coated with a thin gold film and performed by varying the incidence angle with a goniometer.     

蒎烯类苯酚基吡啶氟硼发光材料的合成与性质

将天然刚性结构单元蒎烯引入到苯酚基吡啶氟硼配合物体系中,制备了一系列具有蓝光发射性质的手性氟硼配合物。研究结果表明,蒎烯基团的引入可以提高配合物的荧光量子效率。此外,辅助取代基的变化也能进一步调控配合物的发光性质。基于蒎烯基团的手性,我们还研究了这类氟硼发光配合物对映体的圆二色谱。     

d-f跃迁发光稀土配合物研究进展

稀土配合物独特的发光性质使其在众多领域有很大的应用价值.其中,d-f跃迁发光稀土配合物具有跃迁宇称允许、激发态寿命短和光谱可调等特点,但相关研究还有待进一步深入.本文介绍了稀土配合物的发光机制,综述了具有d-f跃迁发光性质的稀土配合物(主要是Ce3+,Eu2+,Yb2+和Sm2+配合物)的研究进展,并初步总结了配合物分...     

含⊥酰亚胺和8-羟基喹啉双官能团的金属络合物型发光材料

应用 Gabriel反应替代传统的亚酰胺缩合法 ,成功地合成了一种含⊥酰亚胺发色团的金属络合物型发红光材料 (Pery- q) 3 Al,在其结构中引入电子传输功能单元 8-羟基喹啉铝 (Alq3 )。在 (Pery- q) 3 Al体系中 ,由于单线态之间的能量转移 ,导致 Alq3 单元的荧光发生了严重的淬灭     

Luminescent Coordination Polymers Based on Self‐Assembled Cadmium Dipyrrin Complexes

A series of novel Cd^II complexes based on α,β‐unsubstituted dipyrrin ligands (dpm) has been prepared and characterised both in solution and in the solid state. These compounds are of the [Cd(dpm)₂] type, with the coordination sphere of the metal centre occupied by two dpm chelates. Interestingly, in contrast to what has been reported for the Zn^II analogues, in the presence of a pyridyl‐ or imidazolyl‐appended dpm ligand, the coordination number of the Cd^II cation can be increased to six, leading to an octahedral coordination sphere. As a consequence, the formation of 1‐, 2‐, and 3D coordination polymers by self‐assembly is observed. Photophysical investigations of the discrete complexes and self‐assembled networks have demonstrated that both types of compounds are luminescent in the solid state.     

Multicolour Optical Coding from a Series of Luminescent Lanthanide Complexes with a Unique Antenna

The bis‐tetrazolate‐pyridine ligand H₂pytz sensitises efficiently the visible and/or near‐IR luminescence emission of ten lanthanide cations (Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb). The Ln^III complexes present sizeable quantum yields in both domains with a single excitation source. The wide range of possible colour combinations in water, organic solvents and the solid state makes the complexes very attractive for labelling and encoding.     

含苝酰亚胺和8-羟基喹啉双官能团的金属络合物型发光材料

应用Gabriel反应替代传统的亚酰胺缩合法．成功地合成了一种含苝酰亚胺发色团的金属络合物型发红光材料(Pery-q)3Al。在其结构中引入电子传输功能单元8-羟基喹啉铝(Alq3)。在(Pery-q)3Al体系中,由于单线态之间的能量转移。导致Alq3单元的荧光发生了严重的淬灭。     

过渡金属正离子和卡宾配合物成键特征的理论分析

在6—311C基组从头算的基础上对第一过渡系含偶数电子的金属正离子(Sc^+， V^+，Mn^+，Co^+，Cu^+)与卡宾CH2的配合物的成键特征进行了细致的分析。用能 级位移算符逐步降低分子片空轨道能级的方法代替分子片轨道冻结，使KSM能量分 解的耦合项得以消除。能量分析结果表明，Sc^+-CH2键是由σ供键，π供键与π反 馈键组成的，不能忽略π供键。而Cu^+-CH2键是由σ供键与σ，π反馈键组成的， 不能忽略σ反馈键。同时对VCH2^+，MnCH2^+和CoCH2^+的^1A1电子态也进行了粗略 的讨论。     

基于吡嗪-吡啶-酰腙配体的三个配合物的制备及其荧光和光催化性能

合成了3个配合物{[Zn₃（L）₂（SO₄）₂（H₂O）₄]·H₂O}_n（1）、{[Cd₂（L）₂（SO₄）（H₂O）]·H₂O}_n（2）和{[Cd（L）I]·CH₃OH}_n（3）（HL=N''-nicotinoyl-pyrazine-2-carbohydrazonamide）,并通过单晶X射线衍射、红外、元素分析和粉末X射线衍射等手段进行表征。配合物1中,采用μ₃-η¹η¹η¹配位模式的SO₄^2-把Zn（Ⅱ）连接成无机网状二维平面（bc面）,有机配体HL交错的分布在网状平面的两侧,这些二维层在分子间氢键的作用下形成三维超分子结构。配合物2是由配体HL连接[（Cd2）₂（μ₂-SO₄）₂]和Cd1两种节点形成的二维结构,相邻的二维层在π…π堆积作用下形成三维超分子结构。配合物3是一维的Z字链结构,这些一维链在氢键的连接作用下形成二维的超分子网络结构。光催化降解亚甲基蓝实验结果表明,在双氧水存在时配合物1~3均表现出很好的降解效果。