中国超分子聚合物的研究与动态

超分子聚合物是高分子科学与超分子科学交叉的研究方向.超分子聚合物的研究在中国引起了学术界的广泛兴趣,中国的学者们对推动此研究领域的发展做出了贡献,并在新的超分子聚合方法、可控超分子聚合以及功能超分子聚合物等方面取得了一系列重要的创新成果.本文总结和评述了中国超分子聚合物的研究与动态,并展望了超分子聚合物化学、超分子聚合物物理、超分子聚合物表征及功能超分子聚合物的未来发展.     

单分子结的构筑及分子电导性质的测试

分子电子学已成为21世纪研究的热点. 通过将具有特定功能的分子连接在纳米尺度金属电极之间从而构筑包括分子导线、开关、整流器在内的各种分子尺度电子器件, 这引起了科学家们广泛的研究兴趣. 在分子电子学研究中, 构筑金属/分子/金属(MMM)分子结是研究分子器件中电子传输性质的关键. 尽管已经取得了很大的进展, 目前在纳米尺度下构筑稳定可靠的MMM分子结并测试单个分子的电学性质仍然面临很多挑战. 本文着重对单分子电学性质的测试技术和相关理论研究的最新进展以及存在的挑战做了概述.     

关于分子特征形状的理论

借助于分子中电子运动的经典转折点, 定义了分子的内禀特征轮廓. 文中以甲烷、甲醇和甲酸为例, 详细介绍了分子内禀特征轮廓理论方法. 对分子轮廓的特征截面的具体分析, 可以给出形成分子过程中原子的空间变化信息. 首次计算和绘出了上述分子轮廓上的电子密度分布图, 它与分子的化学性质密切相关, 给出了对分子边界的新认识.     

超越分子概念的化学：超分子化学的基础与应用

从超分子化学的起源与发展、超分子体系的分类及其功能与应用3个方面阐述了超分子化学的基本概念、超分子化学与分子化学的区别,以及超分子化学在生活和生产中的应用,并对其发展和应用进行了总结和展望。     

关于分子特征形状的理论--Ⅱ.几个典型有机分子的内禀特征轮廓

借助于分子中电子运动的经典转折点,定义了分子的内禀特征轮廓.文中以甲烷、甲醇和甲酸为例,详细介绍了分子内禀特征轮廓理论方法.对分子轮廓的特征截面的具体分析,可以给出形成分子过程中原子的空间变化信息.首次计算和绘出了上述分子轮廓上的电子密度分布图,它与分子的化学性质密切相关,给出了对分子边界的新认识.     

基于主客体识别的刺激响应型分子梭

分子梭作为分子机器的一种主要类型,大多是建立在主客体识别的基础上的,其在分子开关、分子逻辑门、信息存储等领域有着重要的潜在应用价值,是超分子化学领域的研究热点之一。本文介绍了分子梭的概念、原理,详细归纳了具有刺激响应型的分子梭。并且,按照外界刺激源的不同,将刺激响应型分子梭分为光驱动、pH驱动、氧化还原驱动以及多重驱动的分子梭。阐述了不同驱动方式的分子梭的结构特点、运动规律、研究进展及潜在应用,分析了刺激响应型分子梭目前面临的问题,并对其今后的发展趋势做了展望。     

分子的模糊对称性

将模糊数学方法引入对分子对称点群的研究,建立描述具有不完整分子对称性的模糊点对称群(集合).建立具有模糊对称性分子轨道的模糊表示及其模糊特征标(模糊广义宇称).通过对典型的线状分子、平面分子以及非平面的立体分子等进行分析,展示了一个新的理论化学园地.初步探讨了具有模糊对称性的动态反应体系.从模糊对称性出发,探讨了分子轨道对称守恒原理的半定量特征.     

分子印迹-仿生传感器的研究进展

分子印迹技术是制备具有选择性分子识别能力聚合物(分子印迹聚合物)的新兴化学合成技术。分子印迹聚合物的一个重要应用是在生物传感器中取代生物分子作为识别元件,研制耐受性强、低成本的分子印迹仿生传感器。综述了分子印迹技术的基本原理及其在仿生传感器方面的应用研究现状,并对分子印迹仿生传感器的发展前景进行了评述。引用文献24篇。     

非手性的酞菁铜分子在Bi(111)表面上的手性特征

利用低温扫描隧道显微镜（LT-STM）研究了酞菁铜（CuPc）分子在Bi（111）表面上的吸附和手性自组装结构。由于较弱的分子-衬底相互作用,我们发现在液氮温度（78 K）下吸附在Bi（111）表面上的单个CuPc分子围绕着分子中心发生旋转,直到遇到其他分子形成团簇为止。随着分子覆盖度的增加,CuPc分子形成了自组装分子单层。高分辨STM图表明,非手性的CuPc分子出现了手性特征：两个相对的酞菁基团发生了弯曲。当覆盖度超过一个分子层,酞菁铜分子的吸附取向由“平躺”转变到“站立”姿态。我们认为,酞菁铜分子的手性起源是由两种因素共同导致的结果：一种是分子-衬底之间的非对称电荷转移,另一种是相邻分子间的非对称性的范德华力作用。     

分子印迹聚合物的制备及其传感器应用研究

分子印迹技术于近十年内得到了飞速的发展,已经成为当前研究的热点之一.本文主要介绍了分子印迹聚合物的原理以及一些常用制备方法.分子印迹聚合物的一个重要应用是在化学传感器中作为识别元件,研制稳定、低成本的分子印迹传感器.分子印迹聚合物在传感器领域的应用是分子印迹技术的一个重要方面,本文综述了分子印迹聚合物在化学传感器方面的应用研究现状,并对分子印迹传感器的发展前景进行了评述.     

New cobalt(II) and zinc(II) coordination frameworks incorporating a pyridyl-pyrazole ditopic ligand

The metal-directed assembly of new molecular frameworks incorporating 4-(4-pyridyl)pyrazole (L), containing non-linear coordination vectors, is presented. Three metallo-arrays of types [Co(LH)2(NO3)4], [Co(LH)2(H2O)4][NO3]4.H2O and [Zn2(L-H)2Cl2].2EtOH are reported. The cobalt(II) in [Co(LH)2(NO3)4] displays distorted octahedral geometry, with the two protonated pyridyl-pyrazole ligands coordinated through their pyrazole nitrogen atoms in a trans-orientation; the remaining four coordination sites are occupied by nitrate anions. Two internal hydrogen bonds occur between each pyrazole NH and the oxygens of adjacent coordinated nitrato ligands. Short intermolecular hydrogen bonds also occur between the two pyridinium hydrogens and bound nitrate ligands on different molecules to yield a two-dimensional hydrogen-bonded array. Two of these arrays interpenetrate to form an extended two dimensional layer; such layers stack throughout the crystal structure. A second product of type [Co(LH)2(H2O)4][NO3]4.H2O exists as two crystallographically independent, but chemically similar, forms. In each form, the two protonated pyridyl-pyrazole ligands occupy trans positions about the cobalt, with the remaining four coordination sites being filled by water molecules to yield a distorted octahedral coordination geometry. Intramolecular hydrogen-bonding is observed between the two non-coordinated pyrazoyl nitrogen atoms and bound water oxygen atoms. The third complex, [Zn2(L-H)2Cl2].2EtOH, contains dimer units consisting of two zinc(II) ions bridged by two pyrazoylate groups in which the coordination geometry of each zinc approximates a tetrahedron. Each zinc is bound to two deprotonated pyridine-pyrazole ligands (L-H), one pyridyl group (from a different dimeric unit) and one chloro ligand. Each pyridyl nitrogen thus connects each of these zinc dimers to an adjacent dimer unit, forming a three-dimensional network containing small voids. The latter are occupied by ethanol molecules which form hydrogen bonds to the chloro ligands.     

Metal-organic frameworks

Metal-organic frameworks are a recently-identified class of porous polymeric material, consisting of metal ions linked together by organic bridging ligands, and are a new development on the interface between molecular coordination chemistry and materials science. A range of novel structures has been prepared which feature amongst the largest pores known for crystalline compounds, very high sorption capacities and complex sorption behaviour not seen in aluminosilicate zeolites. The development of synthetic approaches to these materials and investigations of their properties are reviewed.     

Terpyridine-Based 3D Metal–Organic-Frameworks: A Structure–Property Correlation

Design, synthesis, and applications of metal–organic frameworks (MOFs) are among the most salient fields of research in modern inorganic and materials chemistry. As the structure and physical properties of MOFs are mostly dependent on the organic linkers or ligands, the choice of ligand system is of utmost importance in the design of MOFs. One such crucial organic linker/ligand is terpyridine (tpy), which can adopt various coordination modes to generate an enormous number of metal–organic frameworks. These frameworks generally carry physicochemical characteristics induced by the π-electron-rich (basically N-electron-rich moiety) terpyridines. In this minireview, the construction of 3D MOFs associated with symmetrical terpyridines is discussed. These ligands can be easily derivatized at the lateral phenyl (4′-phenyl) position and incorporate additional organic functionalities. These functionalities lead to some different binding modes and form higher dimensional (3D) frameworks. Therefore, these 3D MOFs can carry multiple features along with the characteristics of terpyridines. Some properties of these MOFs, like photophysical, chemical selectivity, photocatalytic degradation, proton conductivity, and magnetism, etc. have also been discussed and correlated with their frameworks.     

羧酸类金属有机框架材料的合成及应用

金属-有机框架材料(Metal-Organic?Frameworks,简称MOFs)是由金属离子（簇）与有机桥接配体通过配位共价键或弱相互作用自组装形成的一类具有分子内孔隙的有机-无机杂化材料。羧酸类MOFs材料中金属中心和有机羧酸配体的可变性导致了其结构和功能的多样性,在气体的吸附与分离、荧光、传感、药物传输以及电催化等多个领域展现了独特的应用前景,并被认为是当今科学上最有前途的材料之一。对于有机配体的选择,从早期易坍塌的含氮杂环类配体过渡到了如今稳定性好的羧酸类配体,解决了不少以前出现的MOFs材料结构单一易坍塌问题。     

Overview of N-Rich Antennae Investigated in Lanthanide-Based Temperature Sensing

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields. To circumvent their low molar light absorption, the incorporation of a light-harvesting antenna is required. This Review provides an overview of the nitrogen-rich antennae in lanthanide-based temperature sensors, emitting in the visible light spectrum, and discusses their temperature sensor ability. The N-rich ligands are incorporated in many different platforms. The investigation of different antennae is required to develop temperature sensors with diverse optical properties and to create a diverse offer for the multiple application fields. Molecular probes, consisting of small molecules, are first discussed. Furthermore, the thermometer properties of ratiometric temperature sensors, based on di- and polynuclear complexes, metal–organic frameworks, periodic mesoporous organosilicas and porous organic polymers, are summarized. The antenna mainly determines the application potential of the ratiometric thermometer. It can be observed that molecular probes are operational in the broad physiological range, metal–organic frameworks are generally very useful in the cryogenic region, periodic mesoporous organosilica show temperature dependency in the physiological range, and porous organic polymers are operative in the cryogenic-to-medium temperature range.     

A Surface Coordination Network Based on Copper Adatom Trimers

Surface coordination networks formed by co‐adsorption of metal atoms and organic ligands have interesting properties, for example regarding catalysis and data storage. Surface coordination networks studied to date have typically been based on single metal atom centers. The formation of a novel surface coordination network is now demonstrated that is based on network nodes in the form of clusters consisting of three Cu adatoms. The network forms by deposition of tetrahydroxybenzene (THB) on Cu(111) under UHV conditions. As shown from a combination of scanning tunneling microscopy, X‐ray photoelectron spectroscopy, and density functional theory calculations, all four hydroxy groups of THB dehydrogenate upon thermal activation at 440 K. This highly reactive ligand binds to Cu adatom trimers, which are resolved by high‐resolution STM. The network creates an ordered array of mono‐dispersed metal clusters constituting a two‐dimensional analogue of metal–organic frameworks.     

Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo‐Polymerization Reaction

Getting suitable crystals for single‐crystal X‐ray crystallographic analysis still remains an art. Obtaining single crystals of metal–organic frameworks (MOFs) containing organic polymers poses even greater challenges. Here we demonstrate the formation of a syndiotactic organic polymer ligand inside a MOF by quantitative [2+2] photopolymerization reaction in a single‐crystal‐to‐single‐crystal manner. The spacer ligands with trans,trans,trans‐conformation in the pillared‐layer MOF with guest water molecules in the channels, undergo pedal motion to trans,cis,trans‐conformation prior to [2+2] photo‐cycloaddition reaction and yield single crystals of MOF containing two‐dimensional coordination polymers fused with the organic polymer ligands. We also show that the organic polymer in the single crystals can be depolymerized reversibly by cleaving the cyclobutane rings upon heating. These MOFs also show interesting photoluminescent properties and sensing of small organic molecules.     

金属有机框架材料在分离分析领域的研究进展

金属有机框架材料是由金属离子节点和有机配体通过配位键连接形成的具有序多孔骨架的材料, 因其具有比表面积大、 孔隙可调及表面性质可控等优点而备受关注. 通过对有机配体和金属离子进行选择及对金属有机框架材料进行后修饰处理, 可实现对金属有机框架材料表面性质的调控, 以提升其选择性吸附及特异性识别等性能, 进而拓展其在分离分析等领域的应用. 本文从金属有机框架材料的表面性质调控出发, 介绍了其表面性质与分离分析性能的关系, 总结了近年来该领域的代表性工作, 并展望了金属有机框架材料在分离分析领域的应用前景.     

Recent advances of application of porous molecular cages for enantioselective recognition and separation

Porous materials with well‐defined pore structures have received considerable attention in the past decades due to their unique structures and wide applications. Most porous materials such as zeolites, metal‐organic frameworks, covalent organic frameworks, and porous organic polymers are extended to infinite frameworks or networks by robust covalent or coordination bonds. Porous molecular cages composed of discrete molecules with permanent cavities are an emerging class of porous material and the discrete molecules assemble into solids by weak intermolecular interaction. In comparison to porous extended solids such as metal‐organic frameworks and covalent organic frameworks, porous molecular cage solids are generally soluble in organic solvents thus allowing solution processing, making them more convenient to apply in many fields. This review mainly focuses on the recent advances of application of porous molecular cages (porous organic cages and metal‐organic cages) for enantioselective recognition and separation from 2010 to present, including gas chromatography, capillary electrochromatography, chiral fluorescent recognition, chiral potentiometric sensing, and enantioselective adsorption. Furthermore, the two important family members of porous molecular cages, porous organic cages and metal‐organic cages, are also discussed.     

Interpenetrated Cage Structures

This Review covers design strategies, synthetic challenges, host–guest chemistry, and functional properties of interlocked supramolecular cages. Some dynamic covalent organic structures are discussed, as are selected examples of interpenetration in metal–organic frameworks, but the main focus is on discrete coordination architectures, that is, metal‐mediated dimers. Factors leading to interpenetration, such as geometry, flexibility and chemical makeup of the ligands, coordination environment, solvent effects, and selection of suitable counter anions and guest molecules, are discussed. In particular, banana‐shaped bis‐pyridyl ligands together with square‐planar metal cations have proven to be suitable building blocks for the construction of interpenetrated double‐cages obeying the formula [M₄L₈]. The peculiar topology of these double‐cages results in a linear arrangement of three mechanically coupled pockets. This allows for the implementation of interesting guest encapsulation effects such as allosteric binding and template‐controlled selectivity. In stimuli‐responsive systems, anionic triggers can toggle the binding of neutral guests or even induce complete structural conversions. The increasing structural and functional complexity in this class of self‐assembled hosts promises the construction of intelligent receptors, novel catalytic systems, and functional materials.