铜(Ⅱ)配位树状高分子的研究进展

介绍了一类由铜配位的树状高分子化合物的配位方式、制备及其催化性质。树状高分子与铜配位方式主要有分子内酰胺键的配位和分子末端的端氨基配位或端酯基配位。同时介绍了铜金属纳米粒子的制备及性质。发现随着其代数的增加，所形成纳米粒子的尺寸逐渐减小，而且大大降低了纳米粒子的团聚现象。并探讨了此类大分子在该领域中的研究和应用前景。     

双四氢呋喃环番荔枝内酯类似物以及annonacin与钙离子配位行为研究

作为结构活性关系研究的一部分，利用NMR配位羟基积分法、配位滴定法以及 紫外平衡移动分光光度法，研究了化合物1～5和钙离子的配位行为，发现羟基所在 碳的绝对构型对配位有明显的影响。     

金属-血清白蛋白的结构研究(Ⅷ)──HSA和BSA中锌离子中心的荧光EXAFS研究

荧光EXAFS数据证实，在HSA和BSA中，锌离子与第一配位层原子的核间距分别为0．201nm和0．203nm，配位数近似为4，很可能为4个氮原子配位，胱氨酸硫原子参与配位的可能性基本排除．     

配位负载金属卟啉的合成及催化氧化环已烷的性能研究

合成了三种与咪唑配体键合的新型载体，并通过其与四苯基卟啉铁和卟啉锰配位得到了改性的负载金属卟啉催化剂。讨论了它们在催化氧化环己烷反应中的稳定性、活性等，结果表明配位负载方式明显提高了金属卟啉的稳定性，其中硅胶配位负载锰卟啉还具有较高的活性。     

金属—血清白蛋白的结构研究（Ⅷ）：HSA和BSA中锌离子中心的…

荧光ＥＸＡＦＳ数据证实，在ＨＳＡ和ＢＳＡ中，锌离子与第一配位层原子的核间距分别为０．２０１ｊｍ和０．２０３ｎｍ，配位数近似为４，很可能为４个氮原子配位，胱氨酸硫原子参与配位的可能性基本排除。     

基于培养创新能力的配位化学课程改革的研究与实践

配位化学是化学学科中最具活力和创新性的前沿学科之一，发展迅速且研究内容丰富。而与之相对应的传统配位化学课程则教学内容陈旧，教学方式以教师讲授理论知识为主，缺乏对学生创新能力的培养。为此，从配位化学的教学内容、教学方法和成绩评定方法等方面出发，优化了配位化学课程体系，并通过分析最新研究成果，在总结前人创新思维的同时，利用探究式教学模式，循序渐进地培养学生的创新能力。在期末的综合测评中，学生成绩逐年提高，教学改革取得了良好的教学效果。     

羧基配位结构——共面与非共面

综述了羧酸配合物中出现的羧基的共面配位形式，并着重介绍一种新发现的羧基配位形式———非共面配位。     

氢氧化2,9,16,23-四羧基酞菁铁(Ⅲ)与咪唑轴向配位反应热力学研究

研究卟啉铁与咪唑的轴向配位反应有助于人们探究天然卟啉铁配位的生理反应机理。由于酞菁铁的结构与卟啉铁的结构相似，以酞菁铁为模型化合物的研究也是该领域的热点。本文研究了对四羧基酞菁铁与咪唑的轴向配位反应，在二甲基亚砜溶剂中，测定了不同温度下酞菁铁与咪唑轴向配位反应的平衡常数K值，求得了反应的标准摩尔焓变△rHm^φ瞬和标准摩尔变△rSm^φ。     

硼酸与多羟基化合物配位反应的热化学研究

用量热法在298.2 K测定了B(OH)~-_4与多羟基化合物的反应焓。计算了硼酸与多羟基化合物的配位焓和配离子的标准生成焓。根据配位焓确定了B(OH)~-_4与甘露醇、山梨醇、丙三醇、葡萄糖等多羟基化合物配位反应的配位数，B(OH)~-_4与甘露醇、山梨醇的配位数是2；与丙三醇、葡萄糖的配位数是1．     

MoCo/Y, MoNi/Y氮化物催化剂的结构和CH4+CO2重整反应性能

采用氨气还原法制备了NaY分子筛负载的MoCo/Y、MoNi／Y双组氮化物催化剂，用XRD和EXAFS方法征了样品的结构，并测定了其在CH4＋CO2重整反应中的活性，在氧化态时，MoCo/Y样品中主要存在CoMoO4和Co3O4两种物相，Mo的配位状态接近于CoMoO4，而Co的配位状态更接近于Co3O4，MoNi／Y样品中主要有NiMoO4和NiO两种物相，Mo的配位状态接近于MiMoO4，而Ni的配位状态可能是NiMoO4和NiO两种化合物中Ni配位状态的平均效果，Ni-Mo之间的朴素作用似乎比Co-Mo相对较强，在氮化态时，两种样品中Mo的配位状态较为相似，但即不同于MoO3，也不同于单组分γ－Mo2N.Co和Ni的配位状态都不同于各在氧化态下的状态，且都在相同的位置出现一个新强峰，这似乎表明MoCo和MoNi生成了结构相似的氮化物，在CH4＋CO2重整反应中，氮化态MoCO/Y和MoNi/Y的活性大大超过非负载单组分γ－Mo2N催化剂，其中MoNi/Y的活性相对更好一些，且活性随Ni含量增加而提高。     

Recent advances in biosensory and medicinal therapeutic applications of zinc(II) and copper(II) coordination complexes

Historically, Lewis acidic metal coordination complexes have played a pivotal and defining role in the broad field of molecular recognition and more specifically in the sensing and sequestration of biologically relevant anionic species. More recently, with the expanding interest in chemical biology, there has been a resurgence in the use of coordination complexes, specifically, through their application as medicinal therapeutics and chemo/biosensors. From the disruption of oncogenic protein–protein interactions to the fluorescent sensing of PTP1B phosphatase enzyme activity, the powerful binding potency of coordination complexes has been harnessed to great effect. The ingenuity of the rationally designed coordinating ligands has facilitated the diversity of roles played by Lewis metal complexes. Herein, we will review the recent advances in the application of coordination complexes in medicinal and chemo/biosensory roles over the last decade. In particular, this review will focus on Cu(II) and Zn(II) coordination complexes.     

配位聚合物

配位聚合物是通过过渡金属和有机配体的自组装而形成的 ,它结合了复合高分子和配位化合物两者的特点 ,表现出其独特的性质 ,在非线性光学材料、磁性材料、超导材料及催化等诸多方面都有极好的应用前景。本文根据有机配体种类的不同 ,将配位聚合物分为五大类 ,以便于对它们进行研究。1.含氮杂环类配体的配位聚合物 ;2.含CN有机配体的配位聚合物 ;3.含氧有机配体的配位聚合物 ;4.通过两种配体与一种金属组装成的配位聚合物 ;5.两种以上的金属与相应的配体组装而成的配位聚合物。     

Synthesis and Characterization of Bis(pyridylimino)isoindolide Alkali Metal Complexes in Three Redox States

Non-innocent ligands (NILs) like bis(pyridylimino)isoindolide (BPI) play crucial roles in coordination chemistry, biosciences, catalysis and material sciences. Investigating the isolated redox states of NILs is inevitable for understanding their redox-activity and fine-tuning the properties of corresponding metal complexes. The limited number of fundamental studies on the coordination behavior and redox chemistry of reduced BPI species is suggested to hamper further applications of the title compounds. This work describes for the first time the isolation of alkali metal complexes of BPI and Me₂BPI in three different oxidation states and their characterization by means of NMR or EPR spectroscopy, DFT calculations, and SC-XRD studies. The latter revealed the connection between bond orders in the ligand scaffold and its oxidation state. The paramagnetic compound Me₂BPI-K₂ was isolated as a coordination copolymer with 18-crown-6, which enabled the characterization of the dianionic BPI radical. Furthermore, the so-far unknown trianionic state of BPI was reported by the isolation of BPI-K₃. This divulges an unprecedented bis(amidinato)isoindolide coordination mode.     

Controlling self-assembly of zinc(II)-benzoate coordination complexes with 1,4-bis(4-pyridyl)ethane by varying solvent and ligand-to-metal ratio: Their catalytic activities

Four new coordination polymers formed by zinc-benzoate with the 1,2-bis(4-pyridyl)ethane (bpe) bridging ligand have been prepared and characterized. Zinc-benzoates can be rationally tuned to form four different structures with a bridging bpe ligand by controlling ligand-to-zinc-benzoate molar ratios and by using different solvent systems, and reveal three coordination polymers having similar one-dimensional characteristics but having different mono-, di-, trinuclear nodes (1–3), and a dinuclear ring type molecule (4). This work reveals that the ligand-to-metal ratio and solvent play very important roles in the formation of different coordination structures. We have also shown that the compounds 1–4 catalyzed efficiently the transesterification of a variety of esters. The complex 3 showed the most efficient reactivity and is the best among the catalytic efficiencies reported previously with zinc-containing coordination and polymeric compounds. The substrates with the electron-withdrawing substituents have undergone faster transesterification than those with the electron-donating ones. In addition, the scope of the application of 1–4 as transesterification catalysts has been expanded to now include ethanol and propanol, suggesting that this catalytic system can be potentially useful for preparing various esters by transesterification. Moreover, the transesterification reaction mechanism was discussed by ¹H NMR study.     

一氧化氮、一氧化碳与血红素的配位化学及其生理作用

NO和CO是新近发现的具有重要生理作用的生物活性小分子，其特定的生理效应主要是通过与生物体内血红素蛋白的配位作用产生的。本文比较了NO、CO、O2与高铁血红素、亚铁血红素的配位化学性质，以及它们与亚铁血红素配位所产生的反位效应，简述了这些配位化学性质与生理作用的相关性。     

Synthesis of Monocrystalline Nanoframes of Prussian Blue Analogues by Controlled Preferential Etching

Metal cyanide coordination compounds are recognized as promising candidates for broad applications because of their tailorable and adjustable frameworks. Developing the nanostructure of a coordination compound may be an effective way to enhance the performance of that material in application‐based roles. A controllable preferential etching method is described for synthesis of monocrystalline Prussian blue analogue (PBA) nanoframes, without the use of organic additives. The PBA nanoframes show remarkable rate performance and cycling stability for sodium/lithium ion insertion/extraction.     

A new Cu~(2+)-induced color reaction of a rhodamine derivative N-(3-carboxy)acryloyl rhodamine B hydrazide

A new rhodamine derivative,N-(3-carboxy)acryloyl rhodamine B hydrazide(CARB),has been synthesized,and its unusual spectroscopic reaction with Cu2+ has been investigated.The derivative exhibits a rapid and reversible non-fluorescent absorption upon coordination to Cu2+,which is a rather unusual phenomenon for rhodamine B derivatives.Stoichiometric measurements using the Job's method and the molar ratio method reveal that one CARB molecule combines two Cu2+ ions,and the two Cu2+ ions play different roles:one ...     

Solvent‐Controlled Construction of Two 3D Manganese(II) Coordination Polymers Based on Flexible Tripodal Multicarboxylate Linker and Rod‐Shaped SBUs

To further explore the coordination possibilities of the flexible tripodal ligand, 4,4′,4′′‐(benzene‐1,3,5‐triyl‐tris(oxy))tribenzoic acid (H₃BTTB), two solvent‐controlled three‐dimensional (3D) manganese(II) coordination polymers, [Mn₃(BTTB)₂(H₂O)₄](H₂O)₂ ( 1 ) and [Mn₃(BTTB)₂(DMF)₂](DMF)₂ ( 2 ), were synthesized and characterized. Single crystal X‐ray diffraction analysis indicates that in the Mn^II complexes the BTTB ligands exhibit two coordination modes, which have not been reported previously. Complexes 1 and 2 involve different one‐dimensional (1D) rod‐shaped metal–carboxylate secondary building units (SBUs). The 1D SBUs are further extended to afford two different three‐dimensional (3D) frameworks with similar flu topology via linkage of the BTTB ligands. The results demonstrate that the reaction solvent as well as conformation and coordination mode of BTTB ligands play key roles on the formation of the final framework structures. Additionally, their luminescent properties were investigated.     

Solvent-induced controllable synthesis, single-crystal to single-crystal transformation and encapsulation of Alq3 for modulated luminescence in (4,8)-connected metal-organic frameworks

In this work, for the first time, we have systematically demonstrated that solvent plays crucial roles in both controllable synthesis of metal-organic frameworks (MOFs) and their structural transformation process. With solvent as the only variable, five new MOFs with different structures have been constructed, in which one MOF undergoes solvent-induced single-crystal to single-crystal (SCSC) transformation that involves not only solvent exchange but also the cleavage and formation of coordination bonds. Particularly, a significant crystallographic change has been realized through an unprecedented three-step SCSC transformation process. Furthermore, we have demonstrated that the obtained MOF could be an excellent host for chromophores such as Alq3 for modulated luminescent properties.     

Molecular simulation study of temperature effect on ionic hydration in carbon nanotubes

Molecular dynamics simulations have been performed to investigate the hydration of Li(+), Na(+), K(+), F(-), and Cl(-) inside the carbon nanotubes at temperatures ranging from 298 to 683 K. The structural characteristics of the coordination shells of ions are studied, including the ion-oxygen radial distribution functions, the coordination numbers, and the orientation distributions of the water molecules. Simulation results show that the first coordination shells of the five ions still exist in the nanoscale confinement. Nevertheless, the first coordination shell structures of cations change more significantly than those of anions because of the preferential orientation of the water molecules induced by the carbon nanotube. The first coordination shells of cations are considerably less ordered in the nanotube than in the bulk solution, whereas the change of the first coordination shell structures of the anions is minor. Furthermore, the confinement induces the anomalous behavior of the coordination shells of the ions with temperature. The first coordination shell of K(+) are found to be more ordered as the temperature increases only in the carbon nanotube with the effective diameter of 1.0 nm, implying the enhancement of the ionic hydration with temperature. This is contrary to that in the bulk solution. The coordination shells of the other four ions do not have such behavior in the carbon nanotube with the effective diameter ranging from 0.73 to 1.00 nm. The easier distortion of the coordination shell of K(+) and the match of the shell size and the nanotube size may play roles in this phenomenon. The exchange of water molecules in the first coordination shells of the ions with the solution and the ion diffusion along the axial direction of the nanotube are also investigated. The mobility of the ions and the stability of the coordination shells are greatly affected by the temperature in the nanotube as in the bulk solutions. These results help to understand the biological and chemical processes at the high temperature.