基于非对称噁二唑或三氮唑衍生物配体的配位聚合物构筑
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摘要
本论文围绕当前配位聚合物化学的研究热点,设计并合成了含有功能化噁二唑或三氮唑基团的非对称有机配体,并将其用于定向组装具有预期结构和功能的配位聚合物,在晶体结构表征和性能研究的基础上,初步探讨了部分配聚物的结构-性能关系。全文共分为六章:
第一章首先介绍了此项工作的研究背景,重点介绍了多孔金属-有机配位聚合物(MOFs)的研究进展及其在磁学、光学、催化、吸附与存储方面的应用;并在此基础上提出了本论文选题的依据、目的及所取得的进展。
第二章首次利用5-(4-吡啶基)-1,3,4-噁二唑-2-硫醇(4-Hpyt)与ZnII和CdII反应得到四个具有不同维度的MOFs。配体呈现硫代酰胺和硫醇盐两种异构体以及四种不同的配位模式。晶体结构研究表明在室温和溶剂热条件下可得到不同的结晶产物;常温下得到的锌和镉配聚物含有较大的溶剂通道,进一步研究了它们的溶剂以及氮气吸附性质。第三章利用4-Hpyt或3-Hpyt与典型的八面体CoII(或NiII)离子反应,得到一系列具有不同孔穴尺寸的多孔配聚物,通式为{[M(pyt)2(H2O)2]·(solvents)}n(5?10),呈现出相似的二维主体框架,包结的客体分子依反应媒质而异,其中8中含有少见的四元水簇。第四章合成了两个羧酸类衍生物配体5-(4-吡啶基)-1,3,4-噁二唑-2-硫代乙酸(4-Hpyoa)和其3位吡啶基异构体,将之与金属离子反应得到11?15。它们分别呈现一维双链、二维同手性层、三维锐钛矿或金红石拓扑网络,拓扑结构的多样性取决于金属-配体间的协同作用。
第五章设计了具有三脚架结构的双(1,2,4-三氮唑-1-基)乙酸(Hbtza)配体,将之与八面体金属及d10银离子反应,分别得到(3,6)-连接网络结构的配位聚合物16?18及4-连接三维化合物19。对此系列2D或3D金属-有机框架研究表明构建可靠的分子模块能够形成预定拓扑节点的超分子网络。第六章设计了多齿酰胺类配体N-(3,5-双(3-吡啶基)-1,2,4-三氮唑-4-烟酰胺(3-Hbptza),在草酸根共配体存在下与八面体金属反应,得到两类未见文献报道的(4,5)-连接二维氢键(20?22)或配位(23)拓扑网络。金属离子半径的大小对配体配位模式以及超分子拓扑结构具有重要影响。
On the focus of current hot research topic of coordination polymer, several un-symmetric ligands with functionalized oxadiazole or triazole groups were choosen and applied as predesigned molecular building blocks to achieve the controlled as-semblies of functional coordination polymers through modular synthetic methodology. A series of polymeric complexes were synthesized and structurally characterized, and their properties have also been investigated for the sake of exploiting the potential re-lationship between structures and properties. This thesis consists of six chapters.
In chapter 1, the recent research progress of porous metal-organic frameworks (MOFs) was represented and their useful properties, such as magnetic ordering, opti-cal activity, catalysis ability, and microporosity, were also introduced. Then the re-search significance and main conclusion of this thesis were summarized.
In chapter 2, four novel ZnII and CdII metal-organic coordination polymers based on a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol (4-Hpyt) have been successfully prepared under different conditions. The anionic ligand 4-pyt takes thioamide form in 1, 2 and 4; but the thiolate form in 3. Four types of coordination modes have been detected. Complexes 2 and 4 display large 1-D channels in which the solvents are accommodated. Their adsorption properties of solvent and nitrogen have been also investigated. In chapter 3, reactions of 4-Hpyt or 3-Hpyt with typical octahedral metal ions (CoII or NiII) generate a series of porous coordination polymers with the general formula of {[M(pyt)2(H2O)2]·(solvents)}n (5-10). These crystalline materials behave uniform 2-D grid-like host coordination frameworks with the inclu-sion of varied guest solvents, in one of which unusual water clusters are observed. Chapter 4 presents the structural assemblies of coordination polymers 11-15 by utiliz-ing the familiar metal ions with two flexible and versatile pyridinecarboxylate deriva-tive ligands as the anionic building blocks, namely, 5-(4-pyridyl)-1,3,4-oxadiazole-2- thioacetate (4-Hpyoa) and its 3-N-pyridyl isomer. These complexes display multifari-ous polymeric coordination frameworks, such as 1-D double-strand chain, 2-D ho-mochiral layer, as well as 3-D (3,6)-connected networks with anatase or rutile topol-ogy. Apparently, the metal centers and ligand spacers play a synergistic role in facili-tating the structural diversity.
In chapter 5, a series of two-dimensional (2D) and three-dimensional (3D) MOFs 16–19 with unusual (3,6)-connected or 4-connected SrAl2 net topology are presented on the basis of a predesigned three-connected component bis(1,2,4-triazol-1-yl)acetate (btza). When properly treated with the familiar divalent metal ions, btza may perfectly furnish the coordination spheres for effective connectivity to produce diverse (3,6)-connected nets. In chapter 6, N-(3,5-bis(3-pyridyl)-1,2,4-triazole-4-yl)nicoti-namide (3-Hbptza) was employed to react with octahedral metal ions in virtue of ox-alate co-ligand, and two unprecedented architectures with (4,5)-connected net topol-ogy were afforded in virture of hydrogen-bonding (20?22) or coordination (23) inter-actions. The radii of different metal ions have significant influence on the coordina-tion modes of 3-bptza and the overall supramolecular networks.
第一章首先介绍了此项工作的研究背景,重点介绍了多孔金属-有机配位聚合物(MOFs)的研究进展及其在磁学、光学、催化、吸附与存储方面的应用;并在此基础上提出了本论文选题的依据、目的及所取得的进展。
第二章首次利用5-(4-吡啶基)-1,3,4-噁二唑-2-硫醇(4-Hpyt)与ZnII和CdII反应得到四个具有不同维度的MOFs。配体呈现硫代酰胺和硫醇盐两种异构体以及四种不同的配位模式。晶体结构研究表明在室温和溶剂热条件下可得到不同的结晶产物;常温下得到的锌和镉配聚物含有较大的溶剂通道,进一步研究了它们的溶剂以及氮气吸附性质。第三章利用4-Hpyt或3-Hpyt与典型的八面体CoII(或NiII)离子反应,得到一系列具有不同孔穴尺寸的多孔配聚物,通式为{[M(pyt)2(H2O)2]·(solvents)}n(5?10),呈现出相似的二维主体框架,包结的客体分子依反应媒质而异,其中8中含有少见的四元水簇。第四章合成了两个羧酸类衍生物配体5-(4-吡啶基)-1,3,4-噁二唑-2-硫代乙酸(4-Hpyoa)和其3位吡啶基异构体,将之与金属离子反应得到11?15。它们分别呈现一维双链、二维同手性层、三维锐钛矿或金红石拓扑网络,拓扑结构的多样性取决于金属-配体间的协同作用。
第五章设计了具有三脚架结构的双(1,2,4-三氮唑-1-基)乙酸(Hbtza)配体,将之与八面体金属及d10银离子反应,分别得到(3,6)-连接网络结构的配位聚合物16?18及4-连接三维化合物19。对此系列2D或3D金属-有机框架研究表明构建可靠的分子模块能够形成预定拓扑节点的超分子网络。第六章设计了多齿酰胺类配体N-(3,5-双(3-吡啶基)-1,2,4-三氮唑-4-烟酰胺(3-Hbptza),在草酸根共配体存在下与八面体金属反应,得到两类未见文献报道的(4,5)-连接二维氢键(20?22)或配位(23)拓扑网络。金属离子半径的大小对配体配位模式以及超分子拓扑结构具有重要影响。
On the focus of current hot research topic of coordination polymer, several un-symmetric ligands with functionalized oxadiazole or triazole groups were choosen and applied as predesigned molecular building blocks to achieve the controlled as-semblies of functional coordination polymers through modular synthetic methodology. A series of polymeric complexes were synthesized and structurally characterized, and their properties have also been investigated for the sake of exploiting the potential re-lationship between structures and properties. This thesis consists of six chapters.
In chapter 1, the recent research progress of porous metal-organic frameworks (MOFs) was represented and their useful properties, such as magnetic ordering, opti-cal activity, catalysis ability, and microporosity, were also introduced. Then the re-search significance and main conclusion of this thesis were summarized.
In chapter 2, four novel ZnII and CdII metal-organic coordination polymers based on a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol (4-Hpyt) have been successfully prepared under different conditions. The anionic ligand 4-pyt takes thioamide form in 1, 2 and 4; but the thiolate form in 3. Four types of coordination modes have been detected. Complexes 2 and 4 display large 1-D channels in which the solvents are accommodated. Their adsorption properties of solvent and nitrogen have been also investigated. In chapter 3, reactions of 4-Hpyt or 3-Hpyt with typical octahedral metal ions (CoII or NiII) generate a series of porous coordination polymers with the general formula of {[M(pyt)2(H2O)2]·(solvents)}n (5-10). These crystalline materials behave uniform 2-D grid-like host coordination frameworks with the inclu-sion of varied guest solvents, in one of which unusual water clusters are observed. Chapter 4 presents the structural assemblies of coordination polymers 11-15 by utiliz-ing the familiar metal ions with two flexible and versatile pyridinecarboxylate deriva-tive ligands as the anionic building blocks, namely, 5-(4-pyridyl)-1,3,4-oxadiazole-2- thioacetate (4-Hpyoa) and its 3-N-pyridyl isomer. These complexes display multifari-ous polymeric coordination frameworks, such as 1-D double-strand chain, 2-D ho-mochiral layer, as well as 3-D (3,6)-connected networks with anatase or rutile topol-ogy. Apparently, the metal centers and ligand spacers play a synergistic role in facili-tating the structural diversity.
In chapter 5, a series of two-dimensional (2D) and three-dimensional (3D) MOFs 16–19 with unusual (3,6)-connected or 4-connected SrAl2 net topology are presented on the basis of a predesigned three-connected component bis(1,2,4-triazol-1-yl)acetate (btza). When properly treated with the familiar divalent metal ions, btza may perfectly furnish the coordination spheres for effective connectivity to produce diverse (3,6)-connected nets. In chapter 6, N-(3,5-bis(3-pyridyl)-1,2,4-triazole-4-yl)nicoti-namide (3-Hbptza) was employed to react with octahedral metal ions in virtue of ox-alate co-ligand, and two unprecedented architectures with (4,5)-connected net topol-ogy were afforded in virture of hydrogen-bonding (20?22) or coordination (23) inter-actions. The radii of different metal ions have significant influence on the coordina-tion modes of 3-bptza and the overall supramolecular networks.
引文
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