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第二篇：论文中英文摘要格式

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论文中英文摘要格式

作者姓名：王新龙

论文题目：缠结网络的合成、结构和拓扑类型研究

作者简介：王新龙，男，19xx年06月出生，20003年9月师从于东北师范大学王恩波教授，于20xx年12月获博士学位。

中 文 摘 要

缠结现象是宏观世界中普遍存在的现象，例如奥运会徽标中相互交织的五环、奥迪车标中互相嵌套的四环以及日常生活中的锁链等，在几何学中缠结现象也有体现，比如著名的Borromean环等。然而在微观世界中，这种缠结现象由于其自身结构的特殊性而显得并不普遍。缠结网络是指在配位网络中各个组成部分通过相互连锁和交织等方式构筑的更为复杂的分子扩展体系,例如DNA中的双螺旋结构、轮烷、锁烃和分子结等。从结构特点出发，缠结网络可以分为互穿网络，自穿网络和新类型缠结网络三种类型,其中互穿网络是目前报道最多的缠结类型，而自穿网络(又称多结)和新类型的缠结网络(包括多连锁，多轮烷，多线穿等)却极少被报道。有些缠结类型虽然已通过几何学的方法预测到，但至今仍没有实例发现。

化合物的结构决定其性质，缠结网络由于自身结构的特殊性会产生一些特殊的功能特性，大致可分为以下四个方面：（I）由于互穿网络是由几个相同的网络相互穿插而构成的，因此网络的稳定性和骨架刚性会得到大大增强，早在19xx年美国化学家Hoffmannd等人在美国化学会志上发表的研究性论文中就提出互穿的金刚石网络可以作为潜在的超硬材料；（II）缠结网络中的轮烷是一类特殊的分子机器，通常它们由一个固定的环（类似发动机的气缸）和一个活动的线性分子（类似发动机的活塞）组成。当给这类分子强加某些外界刺激时（例如温度、pH值、化学能、电能等），它们就可以象发动机的活塞一样来回运动，从而在分子开关和药物传输等领域有着十分重要的应用前景。目前绝大多数分子机器都属于缠结体系中的轮烷和准轮烷分子；（III）缠结体系可以增加网络的Langmuir比表面积，从而有效提高该类材料的氢气存储能力。自然不喜欢空穴，因此网络中存在的大空穴不是被溶剂分子填充，就是被自身通过互穿的形式填充，人们也因此普遍认为缠结网络对网络的多孔性来说是一大障碍。然而，美国著名化学家Yaghi教授最近的研究表明，互穿网络并不象我们曾经认为的那样糟糕，它反而能有效提高材料的氢气存储能力，高度缠结的金属有机网络甚至可以被设计为高孔材料。Yaghi课题组系统研究了互穿和非互穿的超分子异构体的气体存储能力，结果发现互穿网络的氢气吸附量是非互穿网络的1.5倍左右，而且其氢气吸附能力在结构类似的6个网络中是最大的，其原因是由于互穿把原来大的空穴分成若干个小的空穴，而这种小的空穴更加有利于氢气分子的识别与存储；（IV）缠结网络由于结构的特殊性而被归于“第三代孔材料”范畴。日本著名化学家Kitagawa教授把当今孔材料的发展分为三代：第一代孔材料除去客体分子后骨架会发生坍塌；第二代孔材料具有刚性的微孔框架，除去客体分子后仍可保持永久的孔道，目前这类材料仍然是国际上研究的热点领域之一，最具代表性的是美国

Yaghi教授课题组的工作；第三代类孔材料具有柔性和动力学可控的骨架，能够对外界刺激，例如光、电场以及不同的客体分子等做出反应，可逆地改变隧道或孔，在气体分离、传感器和驱动器等领域具有潜在的应用前景。到目前为止所发现的第三代孔材料全部属于缠结网络，因为这类网络的各个片段之间存在超分子作用，因此在外界条件改变时容易发生伸缩或移动，从而产生柔性和动力学孔道。

本论文致力于利用不同类型的柔性配体与多核金属-氧簇构筑新颖拓扑的缠结网络，研究这类化合物的合成条件及规律、考察网络的拓扑类型、分析网络所属的缠结类型，探索新物质结构和性能间的关系。

多金属氧酸盐是一类重要的多核金属-氧簇，在催化、医药和材料科学领域具有重要的应用前景，因此将多金属氧酸盐引入缠结体系构筑基于多金属氧酸盐的缠结网络将会是一个有重要意义的研究课题，该类化合物将缠结网络的灵活性与多金属氧酸盐独特的物理化学性质融为一体，可望在材料科学领域找到更为广泛的应用。由于多金属氧酸盐大多具有纳米级尺寸，因此在空间结晶时会产生较大空间位阻，使得构筑基于多金属氧酸盐的缠结网络成为当前合成化学面临的挑战之一。在本论文第二章中，我们以Keggin型多金属氧酸盐为建筑单元，构筑了3个基于Keggin结构多金属氧酸盐的新类型缠结网络。化合物

[CuI4(L1)2(L1')2][PMo12O40]·H2O(1)是目前发现的第一例由Keggin型多阴离子参与构筑的分子双层的多连锁网络；化合物[CuI3(L2)3][{CuII(L2)2}{PMo12O40(VO)2}]·H2O (2)是由Keggin型多阴离子参与构筑的三维α-Po网络与二维层连锁形成的新颖多连锁网络，是第一例具有2D＋3D连锁网络，同时该网络还具有轮烷和锁烃的特征；化合物

[CuII(L3)2(H2O)2][CuI2(L3)2][PMo12O40](3)是一个罕见的包裹多金属氧酸盐的三维多轮烷网络，在结构中分子正方形环绕在二重互穿的dia网络上形成奇特的[3]轮烷片段，Keggin型多氧阴离子则以客体的形式存在于多轮烷网络的螺旋隧道中。研究成果发表于：Chem. Commun., 2007, 4245。

另外一类重要的多核金属簇是CuX (X=Cl, Br, I)簇，这类金属簇具有结构的多样性和独有的功能特性，尤其在光化学和光物理方面具有潜在的应用前景。在本论文第三章中，我们将多金属氧酸盐和高核Cu-I簇通过共价键连接，构筑了一个由经典的Keggin多阴离子簇和高核[Cu24I10]簇共价连接的三维(4,12)-连接网络(NH4)[Cu24I10L12][PMoV2MoVI10O40]3 (4)，拓扑类型为(430·630·86)(46)3，其中Keggin多阴离子作为4连接结点，[Cu24I10]簇作为12连接结点桥连12个Keggin型多阴离子。这是首次通过共价键把两个经典的簇状化合物直接键连的例子。文中[Cu24I10]簇是目前报道的第二大的Cu-I簇。化合物4结合了两种经典簇状化合物各自的性质，表现出优异的热稳定性，荧光性质，电化学稳定性和对亚硝酸根的电催化活性，可望成为一种新型的复合型功能材料。研究成果发表于：Angew. Chem. Int. Ed. 2006, 45, 7411。

自穿插网络一直是极少被报道的一种缠结类型，这种类型又形象地被称为多结，其特征为网络中的最小拓扑环被来自同一网络的最小环连锁。在以往报道的缠结体系中，连接数多以3，4，6连接为主，连接数大于6的自穿插网络一直是空白。我们的设计思路是以多核金属-氧簇作为结点，以线性有机配体为连接剂，设法构筑高连接自穿插网络。在本论文第四章中，我们成功合成了2个八连接的三维自穿插网络和一个具有(3,5)-连接的三维自穿插网络。化合物[Zn5(μ3-OH)2(bdc)4(phen)2](5)是以五核Zn-O簇作为第二建筑单元构筑的八连接自穿插网络，这是第一例八连接的三维自穿插网络，同时也是目前为止报道的具有最高连接数的自穿插网络。化合物[Cd3(bdc)3(L)2(H2O)2] (6)是以三核Cd-O簇作为八连接结点构筑的第二例三维八连接自穿插网络，经过检索，化合物5和6是目前国际上报道的唯一两例八连接的自穿

插网络，这两个化合物的发现不仅为探索高连接拓扑提供了一条新的可行性路线，同时也使自穿插网络有了新的发展。化合物[Ni(oba)(bpy)]·2H2O (7)是一例具有(3,5)-连接拓扑的三维自穿插网络，其结构中存在着由线性配体4,4?-bpy筑撑的二重互穿层。同时考察了上述化合物的荧光和磁学性质。研究成果发表于：Angew. Chem. Int. Ed., 2005, 44, 5824 (封面配图论文，热点论文); Chem. Commun., 2005, 4789; Chem. Eur. J., 2006, 12, 2680 (封面配图论文，热点论文)。

在缠结体系中，有一类缠结网络既不归属于互穿体系，也不属于自穿插体系，因此被统称为新类型缠结，这类化合物主要包括(多)连锁，(多)轮烷，聚线穿，插指型网络等，它们的出现极大地丰富了缠结体系。在本论文第五章中，我们利用双核金属簇和单核金属离子为节点，合成了8个新类型的缠结网络。化合物[Cd(bpea)(phen)2] (8)具有单手性纳米管的九重互锁结构，这是迄今为止最高程度的互锁；化合物[Ni2(oba)2(bpy)2(H2O)2]·bpy (9)是由第一例由一维纳米管构筑的平行多连锁结构；化合物[Co(4,4'-bipy)(H2O)4]·(H2bptc)·2H2O (10)和

[Ni(4,4'-bipy)(H2O)4]·0.5 (btc)·H2O (11)是两个由不同结构单元构筑的准多轮烷网络；化合物

[Zn(HBTC)(4,4?-bpy)]n (12)和[Ni3(oba)2(bpy)2(Hoba)2(H2O)2]·bpy·2H2O (13)是目前发现的唯一两例由手臂式二维层构筑的多穿插网络，代表了迄今为止发现的由最高维数的结构单元参与构筑的多穿插结构；化合物[Cd2(bpea)(PT)(phen)2] [Cd(PT)(phen)]·2H2O (14)和

[Zn(H2bptc)(bpy)]·0.5bpdo (15)是两例具有1D+2D?3D和2D?3D拓扑特征的插指形结构。以上报道的这些新类型的缠结网络都是尚未发现或极少报道的缠结类型，同时考察了它们的热稳定性、荧光性质和磁学性质。这些新类型缠结网络的发现对于丰富缠结网络，探究分子间相互作用提供了一些有意义的实验数据。研究成果发表于：Angew. Chem. Int. Ed., 2004, 43, 5036; Chem. Commun., 2004, 378(Most Access Article); Chem. Commun., 2004, 1876; Cryst. Growth Des., 2006, 6, 439; Cryst. Growth Des., 2006, 6, 2061;. Eur. J. Inorg. Chem., 2005, 3418。

互穿网络是缠结体系中发现最早、报道最多的一种缠结类型。互穿网络通常都具有复杂的晶体结构，同时具有晶体学上的美学特征，给人以心旷神怡的美感。在本论文第六章中我们利用双核金属簇和单核金属离子为节点，合成了6个具有互穿类型的缠结网络。化合物

[Zn2(bdc)2(L1)2]·2H2O (16)是单核Zn离子作为四连接结点构筑的具有dia拓扑的三重互穿结构；化合物[Cu(oba)(H2O)]2·0.5H2O (17)是以双核Cu簇作为平面四连接节点构筑的具有lvt拓扑的五重互穿结构，是迄今为止发现的具有lvt拓扑类型的网络中最高程度的互穿，同时在结构中含有九重互锁的螺旋链；化合物[Zn2(INO)4(4,4?-bpy)]·DMF (18)是单核Zn离子作为五连接节点构筑的第一例具有sqp拓扑的二重互穿结构，互穿后仍然含有较大的孔道；化合物

[Zn(bdc)(L1)0.5] (19)和[Zn(bdc)(L2)0.5] (20)是以双核Zn簇作为六连接结点构筑的具有α-Po拓扑的三重互穿结构；化合物[Zn(oba)(L1)0.5] (21)是一例具有(3,4)-连接 (4·6·10)(4·62·103)拓扑的三重互穿网络。同时考察了所合成化合物的热性质和荧光性质。研究成果发表于：Chem. Commun., 2005, 5450; Inorg. Chem., 2004, 43, 1850。

关键词：金属-氧簇；多金属氧酸盐；缠结网络；水热合成；晶体结构；拓扑学

Syntheses, structures, and topological study of entangled networks

Wang Xinlong

ABSTRACT

Entanglement is a ubiquitous phenomenon in macroworld, such as intertwined five loops in Olympic logo, interlocked four circles of Audi symbol, and curb chain in daily life, and it is also can be seen in geometry, such as well-known Borromean ring. However, it is not universal in microworld due to the structural particularity of its own. Entangled frameworks are extended arrays, more complex than their constituents, that are comprised of individual motifs forming, via interlocking or interweaving, periodic architectures infinite in at least one dimension. Concerning the structural characteristic, entangled nets can be classified into three types: interpenetration, self-penetration and new types of entanglements, of which interpenetration is the most common type, while self-penetration (polyknotting) and new types of entanglements including polycatenation, polyrotaxane, and polythreading are rarely reported. Some entangled types have been forecasted through geometry methods, but no real examples have been observed until now. As structure determines property, structural peculiarity of entangled frameworks will enhance the skeleton rigidity and porosity of the whole framework, thereby generating some peculiar functional properties. These functional properties can be sorted into the following four aspects: (I) interpenetrating nets are formed by several interfingering identical subnets, hence stability and rigidity of framework could be strengthen. American chemists Hoffmann et al. ever put forward that interpenetrating diamondoid networks can be considered as potential super-hard materials in his paper published on J. Am. Chem. Soc. in 1994; (II) rotaxanes are considered as particular types of molecular machines within entangled nets. Generally, they are constituted by a fixed ring (like cylinder of a motor) and a mobile linear molecule (like plunger of a motor). The relative positions of their component parts can be induced to change as a result of some external stimulus, such as temperature, pH, chemical or electrical energy and light. Hence, they possess important potential applications in molecular switches and delivery of drug. At present, most molecular machines belong the category of rotaxanes and pseudorotaxanes; (III) entanglement can leads to improvement of Langmuir surface area, hence increasing H2 storage capacity. Nature abhors a vacuum, therefore extra-large cavity of a single network is filled either by solvents or by interpenetration; an aspect that many considered a drawback to porosity. However, the recent study from America chemist Yaghi reveals that entanglement is not quite so bas as once thought, especially with respect to increasing hydrogen volumetric density uptake in metal-organic frameworks (MOFs). Indeed even

highly entangled MOFs can be designed to be highly porous. Yaghi?s group systematically investigated on gas storage capacity of interpenetrating and non-interpenetrating networks that can be viewed as a supramolecular pair of stereoisomers, and found that the volumetric hydrogen uptake of interpenetrating net is 1.5 times as much as non-interpenetrating network, moreover, hydrogen adsorptive capacity of interpenetrating net is the largest among six similar networks. This can be attributed that original large cavity is divided into some small ones by interpenetration, whereas these small cavities are even more favorable to recognition and storage of hydrogen molecules; (IV) entangled frameworks are vested in the category of “the 3rd generation porous materials”. Following a suggestion of Japanese chemist Kitagawa, porous coordination compounds were classified in the three categories, 1st, 2nd, and 3rd generation. The 1st generation compounds have microporous frameworks and show irreversible framework collapse on removal of guest molecules. The 2nd generation compounds have stable and robust porous frameworks, which show permanent porosity without any guest molecules in the pores. At present, the study for this generation materials is still an appealing topic, represented by research of Yaghi?s group. The 3rd generation compounds have flexible and dynamic frameworks, which respond to external stimuli, such as light, electric field, guest molecules, and change their channels or pores reversibly. Therefore, we can expect that this kind of coordination polymers will find applications for gas separation, sensors, and actuators. Up to now, discoverable the 3rd generation compounds all belong to entangled nets. Intermolecular links with weaker interactions produce flexible parts in a framework, which are liable to cause stretch or movement depending on the external perturbations, thus generating flexible and dynamic pores.

The aim of this thesis is to synthesize new types of entanglement networks on the basis of flexible ligands and multi-nuclear metal-oxygen clusters, to study the synthetic conditions and rules for these compounds, analysize the topological types, and to explore the relationships between structures and properties for these new compounds.

Polyoxometalates (POMs), as a unique class of metal-oxide clusters, have many properties that make them attractive for applications in catalysis, biology, magnetism, optics, and medicine. Therefore, introduction of POMs into entangled systems to construct POM-based entangled frameworks will be an important research topic. Such materials should be able to combine the flexible structure feature of entangled nets with the unique physical and chemical properties of POMs, and may find broader applications in the materials science field. However, most POMs have nanoscale sizes that will produce larger steric hindrance in the course of crystallization. As a result, the construction of POM-based entangled networks is one of the most challenging issues in current synthetic chemistry. In the second chapter of this thesis, three new compounds with different new types of entanglement networks have been hydrothermally synthesized based on polyoxometalate

building blocks. Compound [CuI4(L1)2(L1')2][PMo12O40]·H2O (1) is the first POM-pillared double-layered polycatenation network, compound [CuI3(L2)3][{CuII(L2)2}{PMo12O40(VO)2}]·H2O

(2) displays an intricate (2D+3D) polycatenation having both polyrotaxane and polycatenane character, compound [CuII(L3)2(H2O)2][CuI2(L3)2][PMo12O40] (3) presents a remarkable Keggin-encapsulating 3D polyrotaxane network, in which molecular square ?beads? thread onto a twofold interpenetrating diamondoid skeleton to form unexpected [3]rotaxane motifs and nanosized Keggin-type polyoxoanions reside in the helical channels as guests. Research results are published on Chem. Commun., 2007, 4245.

Another important multi-nuclear metal cluster is CuX (X = Cl, Br, I) clusters, which have variety of structural forms and unique functional properties, especially the potential application in photochemistry and photophysics. In the third chapter of this thesis, an unprecedented (4,12)-connected 3D framework with (430·630·86)(46)3 topology assembled from the covalent connection of nanoscaled [Cu24I10L12]14+ cages and Keggin clusters, (NH4)[Cu24I10L12][PMoV2MoVI10O40]3 (4), has been synthesized by hydrothermal method, in which Keggin anions act as four-connected nodes and [Cu24I10] clusters as twelve-connected nodes linking twelve Keggin polyanions. To the best of our knowledge, this work, for the first time, bridges two traditional but distinct nanoclusters via covalent links. [Cu24I10] cluster is the second largest iodocuprate(I) cluster made so far. More importantly, this framework generates a new kind of composite materials that combines the useful properties of the two clusters, such as high thermal stability, excellent photoluminescent and electrochemical properties. Research result is published on Angew. Chem. Int. Ed. 2006, 45, 7411.

Self-penetrating nets have rarely been reported, and they can be called polyknotting having the peculiarity that the smallest topological rings are catenated by other smallest rings belonging to the same net. Self-penetrating nets in previous literature are mostly based on 3, 4, or 6-connected nodes, and no such nets with connectivity exceeding six has been reported up to date. Our synthetic strategy is based on multi-nuclear metal cluster as nodes and linear organic ligands as linkers in an attempt to gain highly connected self-penetrating nets. In the forth chapter in this thesis, three self-penetrating networks with two eight-connected and a (3,5)-connected topologies have been synthesized based on multi-nuclear metal-oxygen clusters as nodes. Compound

[Zn5(μ3-OH)2(bdc)4(phen)2] (5) is the first eight-connected self-penetrating net, in which pentanuclear zinc clusters act as eight-connected nodes, and this net also represents the highest connected topology of known entangled species. Compound [Cd3(bdc)3(L)2(H2O)2] (6) is the second eight-connected self-penetrating net, in which trinuclear cadmium clusters act as eight-connected nodes. As far as we known, compounds 5 and 6 are the only two self-penetrating examples with eight-connected topology. Compound [Ni(oba)(bpy)]·2H2O (7) is a (3,5)-connected

self-penetrating net that is assembled from 4,4?-bpy pillared two-fold interpenetrating sheets. Meanwhile, photoluminecent and magnetic properties of these compounds are studied. Research results are published on Angew. Chem. Int. Ed., 2005, 44, 5824 (cover picture of current journal), Chem. Commun., 2005, 4789, and Chem. Eur. J., 2006, 12, 2680 (cover picture of current journal). Besides interpenetration and self-penetration, some entangled nets in the entangled systems neither fall in the interpenetration nor the self-penetration category; we therefore call them new types of entangled nets which include polycatenate, polyrotaxane, polythreading, and interdigitated networks. Their appearance of them greatly enriches existing entangled systems. In the fifth chapter of this thesis, eight new types of entangled networks have been constructed based on binuclear or mononuclear metals as nodes. Compound [Cd(bpea)(phen)2] (8) is the first nine fold interlocked net constructed by chiral nanotube, compound [Ni2(oba)2(bpy)2(H2O)2]·bpy (9) is the first example of a polycatenated array of 1D nanotubes; compounds [Co(4,4'-bipy)(H2O)4]·(H2bptc)·2H2O (10) and

[Ni(4,4'-bipy)(H2O)4]·0.5(btc)·H2O (11) display pseudo-polyrotaxane architectures constructed by different

arm-shape structural layers, motifs, compounds compounds [Zn(HBTC)(4,4?-bpy)]n (12) (14) and and [Ni3(oba)2(bpy)2(Hoba)2(H2O)2]·bpy·2H2O (13) show polythreading networks constructed by [Cd2(bpea)(PT)(phen)2][Cd(PT)(phen)]·2H2O

[Zn(H2bptc)(bpy)]·0.5bpdo (15) exhibit interdigitated architectures with 1D+2D?3D and 2D?3D topological features. These new types of entangled networks descried above either have never or rarely been reported. Meanwhile, thermal stability and photoluminecent and magnetic properties of these compounds are studied. These new types of entangled nets reported herein not only enrich the area of entanglement but also provide some meaningful experimental data for investigation of intermolecular interactions. Research results are published on Angew. Chem. Int. Ed., 2004, 43, 5036; Chem. Commun., 2004, 378(Most Access Article); Chem. Commun., 2004, 1876; Cryst. Growth Des., 2006, 6, 439; Cryst. Growth Des., 2006, 6, 2061;. Eur. J. Inorg. Chem., 2005, 3418.

Interpenetration is the earliest found entangled type and is the most commonly reported phenomenon in the entangled systems. They generally possess intricate structure and aesthetic qualities which give person an aesthetic feeling. In the sixth chapter of this thesis, six new compounds with interpenetrating networks have been constructed based on binuclear or mononuclear metals as nodes. Compound [Zn2(bdc)2(L1)2]·2H2O (16) is a three-fold interpenetrating network of dia topology based on monoclear zinc ion as four-connected nodes, compound [Cu(oba)(H2O)]2·0.5H2O (17) is a five-fold interpenetrating network with lvt topology based on binuclear cupper units as plane four-connected nodes which represents the highest degree interpenetration of known lvt topological nets, compound [Zn2(INO)4(4,4?-bpy)]·DMF (18) is the first two-fold interpenetrating network with sqp topology based on monoclear zinc ions as five-connected nodes, still having significant void space even interpenetration, compounds

[Zn(bdc)(L1)0.5] (19) and [Zn(bdc)(L2)0.5] (20) are two three-fold interpenetrating networks with α-Po topology based on binuclear zinc units as six-connected nodes, compound [Zn(oba)(L1)0.5]

(21) is a three-fold interpenetrating network with (4·6·10)(4·62·103) topology. Meanwhile thermal and luminescente properties of these compounds have been studied. Research results are published on Chem. Commun., 2005, 5450 and Inorg. Chem., 2004, 43, 1850.

Key words: Metal-oxygen clusters; Polyoxometalates; Entanglement networks; Hydrothermal Synthesis; Crystal Structure; Topology