Syntheses，Structures and Properties of Polynuclear Metal Complexes

摘要多核金属簇合物已经成为当今化学研究中最活跃的研究热点之一，不仅因为它们具有纳米尺寸的分子结构，而且还表现出有趣的光、电、磁和催化性质。但目前的研究绝大多数集中在多核过渡金属簇合物上，多核稀土和多核稀土－过渡金属簇合物的研究相对较少。本论文中，我们在多金属氧酸盐配位聚合物、多核稀土簇合物和多核稀土－过渡金属簇合物的合成、结构与性质方面展开了系统的研究，其主要内容和创新点包括：一多金属氧酸盐配位聚合物的组装调控。(1)通过控制反应的pH值合成了从零维到三维的Keggin型多金属氧酸盐配位聚合物(1-5)和(6-7)；(2)利用不同的阴离子，合成了两个Dawson型多金属氧酸盐配位聚合物（8-9...Abstract Polynuclear metal complexes are enjoying widespread current interest not only because of their nanoscale and aesthetically pleasing molecular structures but also because of their interesting luminescent, electronic, magnetic, and catalytic properties. However, most of the works have so far been focused on polynuclear transistion metal complexes, while polynuclear lanthanide or heterometal...学位：理学博士院系专业：化学化工学院化学系_无机化学学号：1912005140304

Slow Magnetic Relaxation in Sandwich-Type Tetranuclear Dysprosium Complex with TMe Q[6](TMe Q[6]=α, α, δ, δ-Tetramethylcucurbit[6]uril)

报道了2个基于四甲基取代六元瓜环的三明治型四核稀土簇合物,[ln4(μ3-OH)4(μ2-OH)2(H2O)4(nO3)2(TME Q[6])2]·(nO3)4·26H2O(ln=dy,1;ln=Tb,2)。晶体结构分析显示2个簇合物包含2个四甲基取代瓜环夹心的四核稀土立方烷结构,[ln4(μ3-OH)4]8+。磁性研究显示化合物1显示了慢磁弛豫行为。由于六元瓜环配体可以有效的传递能量给稀土铽离子,化合物2具有较好的发光性能。Two TMe Q[6]-supported sandwich tetranuclear complexes, [Ln4(μ3-OH)4(μ2-OH)2(H2O)4(NO3)2(TMe Q[6])2](NO3)4·26H2O(Ln=Dy, 1; Ln=Tb, 2), have been prepared and characterized.Crystal structural analysis reveals that both complexes contain a cubane-like [Ln4(μ3-OH)4]8+cluster core sandwiched between two TMe Q[6] macrocycles.Magnetic investigations indicate that complex 1 displays slow magnetization relaxation.Complex 2exhibits intense photoluminescence owing to the efficient energy transfer from TMe Q[6] ligand to Tb3+ion.国家自然科学基金(nos.21422106;21371144;21431005)资助项

计算化学数据与图形在普通化学教学中的运用

鉴于近化学类的非化学专业院系较少开设物理化学和结构化学课程,他们接触到的计算化学知识十分有限,通过对普通化学教学过程中适当引用一些计算化学的模拟研究内容,有利于开拓学生的视野,调动学生学习积极性,更新普通化学教学内容,培养大学生的思维能力,从而提高教学质量。厦门大学校级教改项目(201718

The Investigation Report on Current Status of Sports Consumption in Xiamen

通过对厦门市各阶层人士进行问卷调查 ,对体育经营企业的经营状况实地了解 ,分析厦门市体育消费现状。在 1998年厦门市家庭年均收入为 2 5 6 6 2元 ,年均体育消费为 75 4.95元。在体育消费种类上以体育物质产品消费为主 ,占消费总额的 6 5 .76 %。激发体育消费的因素主要有 :为了身体的健康、个人兴趣爱好等。影响体育消费的主要因素 :价格较高、没时间等。法人体育消费额达 10 0 0万元 (1998年 ) ,目前正呈良好的发展趋势。In order to investigate the sports consumption in xiamen, a total of 2000 questionnaire have been sent out with 1921 taken back. In 1998, the average family income per year is RMB 25662, while the average sports consumption is RMB 754.95. The expenditure on sports products is about the 65.76% of whole expense. The main factors for stimulating expenditure are for health, personal interests and hobbies. High prices and lack of time hamper people from consumption in Xiamen. Legal person sports consumption occupies a quite percentage and reaches 10 million

Two polymeric 36-metal pure lanthanide nanosize clusters

973 Program [2011CBA00507, 2011CB932504]; National Natural Science Foundation of China [21131006]; Natural Science Foundation of Fujian ProvinceTwo rarely seen 2D coordination polymers based on huge 36-metal pure lanthanide clusters, {[Gd-36(NA)(36)(OH)(49)(O)(6)(NO3)(6)(N-3)(3)(H2O)(20)]Cl-2 center dot 28H(2)O}(n) (1) and {[Dy-36(NA)(36)(OH)(49)(O)(6)(NO3)(6)(N-3)(3-)(H2O)(20)]Cl-2 center dot 28H(2)O}(n) (2) (HNA = nicotinic acid), were synthesized and structurally characterized. The spherical Ln(36) skeleton can be viewed as the aggregation of one cyclohexane chair-like Ln(24) wheel and two identical tripod-like Ln(6) units. The coordination of the carboxylic groups of the NA ligands with the Ln(III) cations results in a square layer. Additionally, compound 1 possesses a large MCE of 39.66 J kg(-1) K-1 and compound 2 exhibits slow relaxation of the magnetization

Enantiopure sandwich-type nonanuclear Ln(3)(III)Mn(6)(III) clusters

Three enantiopure isostructural sandwich-type clusters, Ln(3)(III)Mn(6)(III) (Ln = Dy (1), Tb (2) and Gd (3)) have been synthesized through reactions of a chiral Schiff-base ligand ((S, E)-4-( 2-hydroxybenzylideneamino)-2-hydroxybutanoic acid, H(3)L) with manganese and lanthanide ions, showing intramolecular antiferromagnetic interaction.NNSFC[20825103, 90922031, 21021061]; MSTC[2007CB815304]; Natural Science Foundation of Fujian Province of China[2008J0010

Synthesis and Crystal Structure of Coordination Polymer Based on Isonicotinic Acid, Ag(I) and Keggin-Type Polyoxometalate

One Keggin-based complex, [Ag(12)(L)(8)(H(2)O)(5)](SiW(12)O(40))center dot 6H(2)O (1) (L=isonicotinate) was synthesized under hydrothermal condition. The complex was characterized by elemental analysis, IR spectra UV spectra and X-ray single crystal diffraction. The crystal belongs to monoclinic crystal system, space group C2/m with a=1.259 5(2) nm, b=2.429 7(3) nm, c=1.825 7(3) nm, beta=103.794(2)degrees, V=5.425 9(13) nm(3), Z=2. Single crystal structural analysis reveals that the complex is a porous Keggin-based 3D coordination polymer based on the incorporation of void between 2D metal-organic networks and Keggin anion. CCDC: 820578

Keeping the Ball Rolling: Fullerene-like Molecular Clusters

通讯作者地址: Long, LS (通讯作者), Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 3. Univ Arizona, Dept Chem, Tucson, AZ 85721 USA 电子邮件地址: [email protected], [email protected] discovery of fullerenes in 1985 opened a new chapter in the chemistry of highly symmetric molecules. Fullerene-like metal dusters, characterized by (multi)shell-like structures, are one rapidly developing class of molecules that share this shape. In addition to creating aesthetically pleasing molecular Structures, the ordered arrangement of metal atoms within such frameworks provides the opportunity to develop materials with properties not readily achieved in corresponding mononuclear or lower-nuclearity complexes. In this Account, we survey the great variety of fullerene-like metal-containing clusters with an emphasis on their synthetic and structural chemistry, a first step in the discussion of this fascinating field of cluster chemistry. We group the compounds of interest into three categories based on the atomic composition of the cluster core: those with formal metal-metal bonding, those characterized by ligand participation, and those supported by polyoxometalate building blocks. The number of clusters in the first group, containing metal-metal bonds, is relatively small. However, because of the unique and complex bonding scenarios observed for some of these species, these metalloid clusters present a number of research questions with significant ramifications. Because these cores contain molecular clusters of precious metals at the nanoscale, they offer an opportunity to study chemical properties at size ranges from the molecular to nanoscale and to gain insights into the electronic structures and properties of nanomaterials of similar chemical compositions. Clusters of the second type, whose core structures are facilitated by ligand participation, could aid in the development of functional materials. Of particular interest are the magnetic clusters containing both transition and lanthanide elements. A series of such heterometallic clusters that we prepared demonstrates diverse magnetic properties including antiferromagnetism, ferrimagnetism, and ferromagnetism. Considering the diversity of their composition, their distinct electronic structures, and the disparate coordination behaviors of the different metal elements, these materials suggest abundant opportunities for designing multifunctional materials with varied structures. The third type of dusters that we discuss are based on polyoxometalates, in particular those containing pentagonal units. However, unlike in fullerene chemistry, which does not allow the use of discrete pentagonal building blocks, the metal oxide-based pentagonal units can be used as fundamental building blocks for constructing various Keplerate structures. These structures also have a variety of functions, including intriguing magnetic properties in some cases. Coupled with different linking groups, such pentagonal units can be used for the assembly of a large number of spherical molecules whose properties can be tuned and optimized. Although this Account focuses on the topological aspects of fullerene-like metal clusters, we hope that this topical review will stimulate more efforts in the exploratory synthesis of new fullerene-like clusters. More importantly, we hope that further study of the bonding interactions and properties of these molecules will lead to the development of new functional materials.NNSFC 20825103 20531050 20721001 MSTC 2007CB875304 U.S. NSF CHE-023879

In situ cyclodehydration of iminodiacetic acid into 2,5-diketopiperazine-1,4-diacetate in lanthanide-based coordination polymers

The reaction of iminodiacetic acid with Ln(2)O(3) (Ln = Dy, Ho, Er, Yb) under hydrothermal conditions generate a series of 3D lanthanide-based coordination polymers, in which, the iminodiacetic acid (IDA) was transformed into a 2,5-diketopiperazine-1,4-diacetate.NNSFC [20825103, 20721001]; MSTC [2007CB815304]; Natural Science Foundation of Fujian Province of China [2008J0010

Construction of polyoxometalates-based coordination polymers through direct incorporation between polyoxometalates and the voids in a 2D network

通讯作者地址: Long, YX (通讯作者), Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Key Lab Analyt Sci,Minist Educ, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Key Lab Analyt Sci,Minist Educ, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] series of polyoxometalates (POMs)-based coordination polymers, namely, {[Cu(2,3-Me(2)pz)(2,5-Me(2)pz)(0.5)](4)-(SiW12O40)(2,5-Me(2)pz)}(n) (2,3-Me(2)pz) =2,3-dimethylpyrazine; 2,5-Me(2)pz = 2,5-dimethylpyrazine; 1), {[Cu-2(4,4'-bipy) (4)(H2O)(4)](SiW12O40)(H2O)(18)}(n) (4,4'-bipy) 4,4'-bipyridine; 2), {[Cu(2-Mepz)(1.5)](3)(PMo12O40)(H2O)(3.5)}(n) (2-Mepz) 2-methylpyrazine; 3), {[Ag(2,3-Me(2)pz)(1.5)](4)(SiW12O40)}(n) (4), {[Cu(pz)(1.5)](4)(SiW12O40)(H2O)(3)}(n) (pz = pyrazine; 5), {[Cu(2,3-Me(2)pz)(1.5)](4)(SiW12O40)}(n) (6), {[Cu(4,4'-bipy)(1.75)](4)(SiW12O40)(H2O) 2}(n) (7), and {[Cu-2(4,4'-bipy)(4)(H2O)(4)](SiW12O40)(4,4'-bipy)(2)(H2O)(4)}(n) (8), were synthesized through direct incorporation between POMs and the voids of the 2D network. Crystal structural analysis reveals that the relationship between the size of the void of the 2D network and that of POMs is of key importance for successful synthesis of POMs-based open metal-organic frameworks. Guest replacement shows that the pore size of the framework constructed through direct incorporation between POMs and the voids of the 2D network is very sensitive to guest molecules