【摘要】：近年來,結(jié)構(gòu)精確的納米金屬團簇是無機化學(xué),材料化學(xué)及物理化學(xué)領(lǐng)域的研究熱點。而高核納米銀簇因為其迷人的結(jié)構(gòu)和優(yōu)異的光物理性能,受到各國化學(xué)研究者的廣泛關(guān)注。但目前對它們的研究大多數(shù)停留在結(jié)構(gòu)層面上,而對于它性質(zhì)的更深一步的探索屈指可數(shù)。另外,相對于單一金屬離子,以多核金屬簇為構(gòu)筑模塊的簇基MOFs更易于實現(xiàn)節(jié)點的定向構(gòu)筑和組裝,從而調(diào)控目標材料的結(jié)構(gòu)和性能,因此格外受到科學(xué)家的青睞。但是目前研究比較多的金屬簇基MOFs主要是金屬-氧簇,比如過渡金屬、為數(shù)不多的Zr(Ti)-氧簇等,而銀簇基MOFs目前鮮有報道。本文主要論述了三個高核的炔基銀簇及以納米巰基銀簇為次級結(jié)構(gòu)單元組裝形成的簇基MOFs,并對它們的結(jié)構(gòu)性能進行深入的研究。第一章為前言,簡要介紹了金屬簇及金屬簇基MOFs特點及存在的問題,概述了它們的發(fā)展研究歷程,同時介紹了一些結(jié)構(gòu)新穎、熒光性能良好的高核納米銀簇以及一些有趣且具有廣泛應(yīng)用前景的配位聚合物。第二章我們選用叔丁基磷酸,叔丁基炔銀以及三氟乙酸銀得到了3個穩(wěn)定的炔基銀簇,[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是一個混價的納米銀簇,化合物3不僅結(jié)構(gòu)新穎,而且具有優(yōu)異的熒光性能。第三章我們采用叔丁硫醇銀配體,苯基磷酸以及bpy(4,4'-聯(lián)吡啶)為原料,得到了以10核納米巰基銀簇為結(jié)點的兩個銀簇基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熒光性能優(yōu)越,并且對多種揮發(fā)性有機溶劑具有熒光響應(yīng)效果,主要表現(xiàn)在不同溶劑蒸氣壓力下,化合物的熒光顏色發(fā)生變化。此外,我們對化合物5在不同氯仿蒸氣壓力下的熒光光譜,X-射線粉末衍射和蒸氣吸附進行了測試和分析,并對化合物5的響應(yīng)機理進行了研究。第四章改變含氮配體,采用三齒含氮配體L_1(2,4,6-三(4-吡啶)-1,3,5-三甲基苯)得到了一個三維結(jié)構(gòu){[(Ag10(StBu)_6(CF_3COO)_4(L_1)6)]?xDMAC]}n(6),它是3,6-連接且形成了二重穿插的結(jié)構(gòu)。這樣的構(gòu)型使它具有良好的穩(wěn)定性,即使脫去客體分子后的骨架依然穩(wěn)定,筆者測試了其變溫?zé)晒夤庾V并拍攝了相應(yīng)的變溫?zé)晒庹掌?結(jié)果表明從83 K到303 K,其熒光由黃色變成黃綠色。
[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. 絎簩绔犳垜浠，

本文編號：2266453