高核纳米银簇及银簇基配位聚合物的组装、结构及性能研究
发布时间：2018-10-12 14:21
【摘要】：近年来,结构精确的纳米金属团簇是无机化学,材料化学及物理化学领域的研究热点。而高核纳米银簇因为其迷人的结构和优异的光物理性能,受到各国化学研究者的广泛关注。但目前对它们的研究大多数停留在结构层面上,而对于它性质的更深一步的探索屈指可数。另外,相对于单一金属离子,以多核金属簇为构筑模块的簇基MOFs更易于实现节点的定向构筑和组装,从而调控目标材料的结构和性能,因此格外受到科学家的青睐。但是目前研究比较多的金属簇基MOFs主要是金属-氧簇,比如过渡金属、为数不多的Zr(Ti)-氧簇等,而银簇基MOFs目前鲜有报道。本文主要论述了三个高核的炔基银簇及以纳米巯基银簇为次级结构单元组装形成的簇基MOFs,并对它们的结构性能进行深入的研究。第一章为前言,简要介绍了金属簇及金属簇基MOFs特点及存在的问题,概述了它们的发展研究历程,同时介绍了一些结构新颖、荧光性能良好的高核纳米银簇以及一些有趣且具有广泛应用前景的配位聚合物。第二章我们选用叔丁基磷酸,叔丁基炔银以及三氟乙酸银得到了3个稳定的炔基银簇,[Ag33(CF_3COO_7(tBuPO_3)_4(tBuC≡C)_(14)(OH)_3(DMF)_3]?CF_3COO(1),[Ag45(CF_3COO)_7(tBuPO_3)8(tBuC≡C)_(15)(Br)_3(DMF)_3](2),[Ag63(P)_2(CF_3COO)_8(tBuPO_3)9(tBuC≡C)19(PO_4)4](3),化合物2是一个混价的纳米银簇,化合物3不仅结构新颖,而且具有优异的荧光性能。第三章我们采用叔丁硫醇银配体,苯基磷酸以及bpy(4,4'-联吡啶)为原料,得到了以10核纳米巯基银簇为结点的两个银簇基MOFs:{[Ag10(StBu)_6(CF_3COO)_2(PhPO_3H)_2(bpy)_2(CH_3CN)_2]}n(4),{[Ag10(StBu)_6(CF_3COO)_2(PhPO_3H)_2(bpy)4·(xSolvents)]}n(5),化合物4和5荧光性能优越,并且对多种挥发性有机溶剂具有荧光响应效果,主要表现在不同溶剂蒸气压力下,化合物的荧光颜色发生变化。此外,我们对化合物5在不同氯仿蒸气压力下的荧光光谱,X-射线粉末衍射和蒸气吸附进行了测试和分析,并对化合物5的响应机理进行了研究。第四章改变含氮配体,采用三齿含氮配体L_1(2,4,6-三(4-吡啶)-1,3,5-三甲基苯)得到了一个三维结构{[(Ag10(StBu)_6(CF_3COO)_4(L_1)6)]?xDMAC]}n(6),它是3,6-连接且形成了二重穿插的结构。这样的构型使它具有良好的稳定性,即使脱去客体分子后的骨架依然稳定,笔者测试了其变温荧光光谱并拍摄了相应的变温荧光照片,结果表明从83 K到303 K,其荧光由黄色变成黄绿色。
[Abstract]:In recent years, nanometallic clusters with precise structure have been the focus of research in inorganic chemistry, material chemistry and physical chemistry. Because of its attractive structure and excellent photophysical properties, high-core silver nanoclusters have attracted wide attention from chemical researchers all over the world. However, at present, most of their studies remain at the structural level, and the further exploration of their properties is limited. In addition, compared with a single metal ion, the clust-based MOFs with polynuclear metal cluster as the building module is more easy to realize the directional construction and assembly of the nodes, thus regulating the structure and properties of the target material, so it is particularly favored by scientists. However, the metal cluster based MOFs is mainly metal-oxygen cluster, such as transition metal, a few Zr (Ti) oxygen cluster, etc. However, silver cluster based MOFs is rarely reported at present. In this paper, three high nucleated arynyl silver clusters and cluster based MOFs, assembled with nano-mercapto silver clusters as secondary structure units are discussed and their structural properties are studied. The first chapter is the preface. The characteristics and problems of metal cluster and metal cluster based MOFs are briefly introduced, their development and research history are summarized, and some novel structures are introduced. High nucleated silver nanoclusters with good fluorescence properties and some interesting and promising coordination polymers. 绗簩绔犳垜浠，
本文编号：2266453
[Abstract]:In recent years, nanometallic clusters with precise structure have been the focus of research in inorganic chemistry, material chemistry and physical chemistry. Because of its attractive structure and excellent photophysical properties, high-core silver nanoclusters have attracted wide attention from chemical researchers all over the world. However, at present, most of their studies remain at the structural level, and the further exploration of their properties is limited. In addition, compared with a single metal ion, the clust-based MOFs with polynuclear metal cluster as the building module is more easy to realize the directional construction and assembly of the nodes, thus regulating the structure and properties of the target material, so it is particularly favored by scientists. However, the metal cluster based MOFs is mainly metal-oxygen cluster, such as transition metal, a few Zr (Ti) oxygen cluster, etc. However, silver cluster based MOFs is rarely reported at present. In this paper, three high nucleated arynyl silver clusters and cluster based MOFs, assembled with nano-mercapto silver clusters as secondary structure units are discussed and their structural properties are studied. The first chapter is the preface. The characteristics and problems of metal cluster and metal cluster based MOFs are briefly introduced, their development and research history are summarized, and some novel structures are introduced. High nucleated silver nanoclusters with good fluorescence properties and some interesting and promising coordination polymers. 绗簩绔犳垜浠，
本文编号：2266453
本文链接：https://www.wllwen.com/shoufeilunwen/boshibiyelunwen/2266453.html
