金属有机框架化合物对溶剂分子和有机小分子荧光识别与传感研究进展

属-有机框架（MOFs）化合物由于其特定的孔道/孔洞结构以及在气体吸附/存储与分离、化学传感、光学、磁学以及荧光检测等方面的良好性能及潜在应用而成为当前人们关心和研究的热点。本文聚焦MOFs在溶剂分子和有机小分子荧光识别及传感方面的研究工作,着重介绍该领域近期的研究进展,并对该领域今后的发展进行了展望。     

金属有机框架化合物对溶剂分子和有机小分子荧光识别与传感研究进展

金属-有机框架(MOFs)化合物由于其特定的孔道/孔洞结构以及在气体吸附/存储与分离、化学传感、光学、磁学以及荧光检测等方面的良好性能及潜在应用而成为当前人们关心和研究的热点。本文聚焦MOFs在溶剂分子和有机小分子荧光识别及传感方面的研究工作,着重介绍该领域近期的研究进展,并对该领域今后的发展进行了展望。     

发光稀土配合物的生物功能分子传感研究进展

基于稀土离子独特的电子组态和有机配体的敏化作用,稀土中心发光的配合物具有发光寿命长、发射峰尖锐和Stokes位移大等特点,可在复杂环境中针对特定的分析物进行快速和便捷的检测。稀土配合物与生物功能分子如生命必需分子、疾病标志物分子和药物分子等相互作用引起其光学信息的变化可以实现对生物功能分子的快速传感,在监测生命体的生理状态和公共卫生安全等方面具有重要的意义。本文综述了稀土配合物针对生物功能分子的传感性质研究进展,讨论了设计稀土配合物材料的传感策略,提出了稀土配合物作为生物功能分子先进传感材料的发展建议。     

动态配位空间的构筑与调控

“配位空间”(Coordination Space)是无机-有机杂化体系中的构筑基元通过配位键连接形成的具有特定结构和功能的空间。这一概念为基于配位键的框架体系的定向构筑与结构-性能调控提供了新的视角。作为典型的无机-有机杂化材料,金属-有机框架(Metal-Organic Framework,MOF)及金属有机笼(Metal-Organic Cage,MOC)等近年来受到广泛关注。这类材料的构筑与性能调控的核心可以认为是对其配位空间的结构设计与性能调控。具有刺激响应性的MOF可展现动态的配位空间,使其在吸附分离、传感、药物投递等方面具有重要的应用前景。本文将以动态金属有机框架的相关研究为基础简述动态配位空间研究的近期进展,包括其动态行为产生的结构基础、诱发因素及相关性能,归纳结构-性能的关系,为相关研究提供参考。     

金属有机骨架材料在传感器中的应用

摘 要 金属有机骨架（Metal Organic Framework,MOFs）是由有机配体与金属离子或金属离子簇通过配位作用自组装而成的一种具有永久孔道性的开放结晶骨架,通常也被称为配位聚合物（PCPS）。因为其较大的比表面积、规整的孔道结构、热稳定性和化学可裁剪性,使其在多个领域具有广阔的应用前景。近年来,随着MOFs在传感领域的发展,许多不同的功能基团被引入到MOFs的孔道中,研制出具有荧光识别性能的MOFs。本论文综述了近几年来基于MOFs的化学传感器在离子识别、PH检测、挥发性有机物和气体检测、爆炸物识别和生物分子检测等关键领域的研究进展,并对MOFs在化学传感器的应用前景进行了展望。     

多孔有机聚合物材料的合成与荧光传感应用

多孔有机聚合物荧光材料既具有孔隙度高的特点,也具有突出的荧光性能.当其骨架上存在与特定分析物(如硝基芳香爆炸物、金属离子、阴离子等)的结合位点时,便赋予其荧光传感的功能.按照不同多孔有机聚合物(POPs)材料的类型,即无定型的多孔有机聚合物材料、晶型含配位键的多孔金属有机框架(MOFs)材料、晶型共价有机框架(COFs)材料,综述了近年来多孔有机聚合物荧光材料的研究新进展,特别是它们基于有机功能分子的设计与合成,及其荧光传感应用.继续从分子层面设计新型的荧光COFs材料是未来可循环使用的高效荧光化学传感器的发展方向,值得关注.     

金属有机骨架材料在传感器中的应用

金属有机骨架(MOFs)是由有机配体与金属离子或金属离子簇通过配位作用自组装而成的一种具有永久孔道性的开放结晶骨架,通常也被称为多孔配位聚合物(PCPS)。因为其较大的比表面积、规整的孔道结构、良好的热稳定性和化学可裁剪性,使其在多个领域具有广阔的应用前景。近年来,随着MOFs在传感领域的发展,许多不同的功能基团被引入到MOFs的孔道中,研制出具有荧光识别性能的MOFs。本论文综述了近几年来基于MOFs的化学传感器在离子识别、pH检测、挥发性有机物和气体检测、爆炸物识别和生物分子检测等关键领域的研究进展,并对MOFs在化学传感器的应用前景进行了展望。     

《金属-有机框架》专辑序言──金属-有机框架:新型多功能材料

<正>金属-有机框架是由金属离子与有机配体通过配位键形成的三维框架材料,是近几十年来配位化学领域中发展较快的新型多功能材料。自上世纪90年代以来,金属-有机框架的研究呈现空前的增长,目前已有大于20000例的金属-有机框架被报道。金属-有机框架可变的金属中心及有机配体使其结构与功能具有多样性。金属中心的选择几乎覆盖了所有金属,包括主族元素、过渡元素和镧系金属。而配体的选择,除了传统的氮杂环和羧酸类配体外,还可以引入一些官能团对其进行修饰,使已获得的金属-有     

8-氨基喹啉取代苯甲酰胺衍生物对汞离子和铜离子的识别

设计合成了可识别金属离子的荧光传感分子8-氨基喹啉取代苯甲酰胺衍生物,通过核磁共振谱和质谱表征其结构;利用其光谱性质研究了该系列物质对过渡金属离子Cu2+,Hg2+,Pb2+,Zn2+,Ni2+和Cd2+的识别性质,初步探讨了其识别机理。实验表明:在乙腈中,8-氨基喹啉苯甲酰胺的吸收光谱在509nm处对Cu2+有响应,溶液由无色变成红色;而其荧光光谱对Hg2+和Cu2+有良好的选择性,荧光增强倍率分别高达368和192,与金属离子形成结合比为1:1配合物。     

环糊精衍生物及包合物构建荧光探针的研究进展

环糊精是超分子化学中的一类重要主体化合物,在药物缓释、化学传感、对映体分离以及新型材料等众多领域都得到了广泛的应用.由于环糊精具有外亲水内疏水的桶形结构,其空腔内可以插入具有识别功能的受体分子或荧光染料,可通过螯合或置换方式实现对目标分子的识别,因此基于环糊精衍生物及包合物构建荧光探针也受到了人们的极大关注.总结了基于环糊精设计合成的荧光探针在检测金属离子、阴离子和分子等方面的应用,重点描述了识别性能和识别机制,为环糊精衍生物及包合物在荧光检测领域的应用提供理论依据.     

Highly stable olefin-Cu(I) coordination oligomers and polymers

Highly stable Cu(I)-olefin coordination oligomers and polymers have been successfully prepared and applied to construct metal-organic frameworks (MOFs) with interesting physical and chemical functions in recent years. In this review, we present the olefin-Cu(I) coordination oligomers and polymers and their novel physical properties. From structure to functions, particular emphasis is placed on the coordination and organometallic chemistry of olefin-Cu(I) coordination oligomers and polymers, their structures and potential applications as solids possessing unusual physical functional properties such as electrochemical, chiral separation, fluorescent sensing and ferroelectricity.     

Molecular tectonics of mixed-ligand metal-organic frameworks: positional isomeric effect, metal-directed assembly, and structural diversification

A series of nine mixed-ligand metal-organic frameworks (MOFs) have been prepared by the combination of a bent dipyridyl linker 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (bpt) and three benzenedicarboxylate isomers (pa = phthalate, ip = isophthalate, and tp = terephthalate), respectively, with different metal ions such as CoII, NiII, CuII, ZnII, and CdII. The framework structures of these neutral polymeric complexes have been determined by the X-ray single-crystal diffraction technique. Structural analysis reveals that the benzenedicarboxylate isomers display versatile coordination modes to manage the metal ions to form 1-D chain or ribbon arrays, which are further extended via the exo-bidentate bpt connectors to give rise to a variety of coordination networks, such as a simple (4,4) layer, 2-D double layer with decorated (4,4) topology, 2-D layer with decorated (3,6) topology, 2-D bilayer with 82.10 topology (2-fold interpenetration), 3-D polythreaded architecture (1-D + 2-D), and 2-fold interpenetrating porous lattice of (4,4) layers. The accessorial secondary interactions such as hydrogen bonding and/or aromatic stacking are also helpful for the extension and stabilization of the final supramolecular aggregates. This work evidently indicates that the isomeric effect of the anionic benzenedicarboxylate is significant in the construction of these network structures, which are also well regulated by the metal centers. The ZnII and CdII MOFs exhibit strong solid-state luminescence emissions at room temperature, which originate differently from intraligand transition or ligand-to-metal charge transfer. Thermal stability of these crystalline materials has been explored by thermogravimetric analysis of mass loss. The 3-D host frameworks of MOFs 8 and 9 show similar porous cavities, and their desorption/adsorption behaviors of guest solvents have also been investigated.     

Ambient Temperature Synthesis and Structural Characterization of Six Transition Metal Acetylenedicarboxylate Coordination Polymers

This work reports the ambient temperature synthesis and structural characterization of six new first row transition metal acetylenedicarboxylate coordination polymers. The Co and two Ni compounds adopt structures in which the octahedral metals are connected into 1D chains via the acetylenedicarboxylate ligand. In contrast the Mn and two Zn compounds adopt 3D metal-organic frameworks; while the Mn compound is non-porous the two Zn structures contain dimeric or trimeric clusters connected into frameworks that are potentially porous. These two anionic metal-organic frameworks are, however, charged balanced by cations siting in their pores which greatly reduces the ability to access their porosity.     

Ionothermal syntheses, crystal structures and properties of three-dimensional rare earth metal-organic frameworks with 1,4-naphthalenedicarboxylic acid

Twelve isostructural rare earth metal-organic frameworks, namely, [Hmim][RE(2)Cl(1,4-NDC)(3)] (RE = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Y (12), Hmim = 1-hexyl-3-methylimidazolium, 1,4-NDCH(2) = 1,4-naphthalenedicarboxylic acid), have been ionothermally synthesized and structurally characterized. The structures feature three-dimensionally anionic frameworks of [RE(2)Cl(1,4-NDC)(3)](n)(n-) with channels in which the Hmim(+) cations are located. The current results are the first ionothermal synthesis of rare earth metal-organic frameworks based on 1,4-NDCH(2) which possess a previously unknown (4,7)-connected 3-nodal network with the Schl?fli symbol of (3(2)·4(2)·5(2))(3(2)·4(9)·5(2)·6(8))(2)(4(3)·6(3))(2). Luminescent and magnetic properties of some of the title compounds have been studied. Thermogravimetric analyses indicated that all these compounds were thermally stable up to ca. 250 °C.     

Influence of halide ions on the chirality and luminescent property of ionothermally synthesized lanthanide-based metal-organic frameworks

Four lanthanide-based metal-organic frameworks, [Emim][Ln(1.5)(2,5-tdc)(2)]Cl(1.5-x)Br(x) (Ln = Nd 1, Eu 2) and [Emim][Ln(2,5-tdc)(2)] (Ln = Nd 3, Eu 4) (2,5-tdc = thiophene-2,5-dicarboxylate, Emim = 1-methyl-3-ethylimidazolium), were synthesized under ionothermal conditions. Compounds 1 and 2 crystallize in the polar space group P2(1)2(1)2, while 3 and 4 crystallize in the central symmetry space group P2(1)/c. Luminescence studies revealed a significantly higher quantum yield of 4 than that of 2, with similar lifetimes. It is clear that the coordination of the halide ions has profound effects on the structures and properties of these lanthanide-based metal-organic frameworks.     

One-, two- and three-periodic metal-organic rotaxane frameworks (MORFs): linking cationic transition-metal nodes with an anionic rotaxane ligand

A new singly charged pyridinium axle was prepared and combined with disulfonated dibenzo[24]crown-8 ether to form a [2]pseudorotaxane. The reaction of this new, anionic ligand with Zn(II) ions, under various crystallization conditions, resulted in the formation of three metal-organic rotaxane framework (MORF) solids; a one-periodic ML coordination polymer and two, two-periodic ML(2) square grid frameworks. The layers of square grids can be pillared to create full three-periodic MORF structures, which have completely neutral frameworks and are porous. These three-periodic materials represent the first examples of neutral porous MOFs in which one (or more) of the linkers is a mechanically interlocked molecule (MIM).     

稀土与L-苯丙氨酸配合物的PH电位法及量热滴定法研究

本文在25℃和0.15mol.dm^-^3(NaCl)离子强度下, 用pH电位法和量热滴定法测定了十五个稀土元素(Y和除Pm外的镧系元素)与L-苯丙氨酸1:1配合物的稳定常数及热力学函数。L-苯丙氨酸通过-CO^-~2和-NH~2与稀土离子配位, 生成较稳定的1:1配合物。配合物稳定性呈"四分组效应"。配合物稳定性顺序中Y的位置向轻稀土方向移动。体系的熵变是配位反应驱动力。离子的去水化在配位反应中起重要作用。     

Turn-on fluorescence in tetraphenylethylene-based metal-organic frameworks: an alternative to aggregation-induced emission

Coordinative immobilization of functionalized tetraphenylethylene within rigid porous metal-organic frameworks (MOFs) turns on fluorescence in the typically non-emissive tetraphenylethylene core. The matrix coordination-induced emission effect (MCIE) is complementary to aggregation-induced emission. Despite the large interchromophore distances imposed by coordination to metal ions, a carboxylate analogue of tetraphenylethylene anchored by Zn(2+) and Cd(2+) ions inside MOFs shows fluorescence lifetimes in line with those of close-packed molecular aggregates. Turn-on fluorescence by coordinative ligation in a porous matrix is a powerful approach that may lead to new materials made from chromophores with molecular rotors. The potential utility of MCIE toward building new sensing materials is demonstrated by tuning the fluorescence response of the porous MOFs as a function of adsorbed small analytes.     

稀土-氨基多羧酸配合物的配位结构及变化规律I氨基三乙酸(nta)、乙二胺四乙酸(edta)和反式-1,2-环己二胺四乙酸(cydta)系列

本文综述了稀土金属离子与一系列氨基多羧酸配体(如nta(=氨基三乙酸),edta(=乙二胺四乙酸),cydta(=反式-1,2-环己二胺四乙酸),dtpa(=二乙三胺五乙酸)和ttha(=三乙四胺六乙酸)等)形成配合物的分子结构和晶体结构,发现了这些配合物的配位规律和结构变化,说明了稀土金属离子象其它过渡金属离子一样,与氨基多羧酸配体形成配合物的配位数和配位结构取决于稀土金属离子的离子半径,电子结构和配体形状以及配电离子等。     

面向丙烯/丙烷吸附分离的金属有机骨架材料的高通量计算筛选

丙烯、丙烷作为分子尺寸相近的共沸物,其分离一直是化工领域研究热点。金属有机骨架(MOFs)材料因其高度可调的孔道结构,在丙烯/丙烷分离应用上已展现出诱人潜能。本文基于Core MOF 2019数据库,采用巨正则蒙特卡洛基高通量计算筛选技术,获得了分离性优异的MOFs结构,发现其拥有适中的丙烯吸附量和较弱的丙烷吸附能力,且骨架孔径为3.70～4.10?、孔隙率中等(0.35～0.44),并揭示了孔道中心吸附位的选择性与丙烯/丙烷分离系数间关系。本研究阐明了高丙烯/丙烷分离性的骨架材料的结构和性能特征,为设计MOFs实现丙烯/丙烷的高效分离提供理论指导和数据支撑。