【作者】 杨璐；

【导师】 魏青；

【作者基本信息】 西北大学 ， 有机化学， 2016， 硕士

【摘要】 本文中,我们以合成的4,4’,4"-三甲酸三苯胺（H₃TCA）为第-配体,以具有发光特性的Eu,Tb,Zn,Cd为中心金属离子,选择不同的第二配体调整主体框架,用水热法合成了8个金属有机骨架（MOFs）,分析了其结构特征,探究了其光学特性及荧光传感行为,具体内容和结论如下：一、以Eu和Tb为中心金属离子,成功合成了两个同构的金属有机骨架：[Eu（TCA）（1,4-ndc）·H₂O]_n（1）,[Tb（TCA）（1,4-ndc）·H₂O]_n（2）（1,4-ndc表示1,4-二萘酸）。结构分析表明,Eu（Tb）离子呈现出九配位的环境,H₃TCA呈现出三种不同的配位模式并桥联周围的Eu（Tb）离子形成三维的网状结构。光学研究表明,配合物2（Tb）与配合物1（Eu）（τ=0.335 ms,Φoverall=0.06%）相比具有较长的发光寿命（r=0.342 ms）和较高的量子产率（Φoverall=11%）；二、以Zn为中心金属离子,成功合成了两例MOFs:[Zn₃（TCA）₂（4,4’-bpp）]_n（3）, [Zn₆（TCA）₄（4,4’-bpt）₃·2H₂O]_n（4）[4,4’-bpp表示1,3-双（4-吡啶基）-丙烷,4,4’-bpt表示3,5-双（4-吡啶基）-1,2,4-三唑]。结构分析表明,配合物3和4的最小不对称单元均包含三个Zn离子,H₃TCA分别呈现出两种和三种配位模式,并且与第二配体共同桥联周围的Zn离子形成三维的结构。研究发现,配合物3可以作为识别Na⁺和Co²⁺的荧光传感器,配合物4对Fe³⁺表现出高度的选择性。三、以Cd为中心金属离子,成功合成了四个不同的金属有机骨架：{[Cd₃（TCA）₂（4,4’-bpp）2]·2DMF.4H₂O}_n（5）,{[Cd₆（TCA）₄（4,4’-bpt）₃·2H₂O]·4DMA·4H₂O}_n （6）,[Cd（TCA）（4,4’-bpy）_0.5]_n（7）,{[Cd₃（TCA）₂（2,2’-bpy）₂·H₂O]·2H₂O}n（8）[4,4’-bpp表示1,3-双（4-吡啶基）-丙烷,4,4’-bpt表示3,5-双（4-吡啶基）-1,2,4-三唑,4,4’-bpy表示4,4’-联吡啶,2,2’-bpy表示2,2’-联吡啶]。结构分析表明,配合物5和6是由三核Cd单元组成的三维结构,H₃TCA均呈现出三种配位模式；配合物7是由单核Cd单元构成的三维结构,H₃TCA只有一种配位模式；配合物8的最小不对称单元中包含三个Cd离子,H₃TCA呈现出两种配位模式并桥联周围的Cd离子形成三维的网络结构。研究发现,配合物5和8对Fe³⁺表现出高度的选择性,配合物6可以作为识别pb²⁺和Cu²⁺的荧光传感器,配合物7可以作为识别Na⁺和Fe³⁺的荧光传感器。更多还原

【Abstract】 In this paper, primary ligand 4,4’,4"-tricarboxytriphenylamine （H₃TCA） was synthesized previously. Then Eu, Tb, Zn and Cd ions are selected as central metal ions and different second ligands are selected to adjust the body frame. Eight metal-organic frameworks were designed and synthesized by hydrothermal method. These compounds have been structurally characterized, and the photoluminescent and luminescent sensors were studied respectively.1. Two isomorphic compounds [Eu（TCA）（1,4-ndc）·H₂O]_n （1）, [Tb（TCA）（1,4-ndc）·H₂O]_n （2） （1,4-ndc= 1,4-naphthalenedicarboxylate） have been synthesized and characterized. Crystal structure analyses show that 1 and 2 display 3D framework in which Eu and Tb cations present nona-coordination geometries. Optical investigation indicates that 2 shows a relatively longer luminescence lifetime （r= 0.342 ms） and significantly enhanced quantum yield （Φoverall= 11%） compared with those of 1 （τ= 0.335 ms,Φovrall= 0.06%）;2. Two MOFs [Zn₃（TCA）₂（4,4’-bpp）]_n （3）, [Zn₆（TCA）₄（4,4’-bpt）₃·2H₂O]n （4） （4,4’-bpp= 4,4’-Trimethylenedipyridine,4,4’-bpt= 3,5-di-（4-pyridyl）-1,2,4-triazoles） have been successfully synthesized. Structure analyses determine that there are three Zn ions in the asymmetric units of compounds 3 and 4 and the H₃TCA ligand presents two and three bridged fashions, respectively. The oxygen atoms in H₃TCA groups and the nitrogen atoms in the second ligands integrate all of the Zn ions, constructing the 3D framework. The researches show that compound 3 provides an ideal luminescence sensor for high selective probing Na+ and Co²⁺ions and compound 4 displays high selectivity for Fe³⁺ion.3. Four new metal-organic frameworks{[Cd₃（TCA）₂（4,4’-bpp）₂]·2DMF-4H₂O}_n （5）, {[Cd₆（TCA）₄（4,4’-bpt）₃·2H₂O]·4DMA·4H₂O}_n （6）, [Cd（TCA）（4,4’-bpy）_0.5]_n （7） and {[Cd₃（TCA）₂（2,2’-bpy）₂·H₂O]·2H₂O}_n （8） （4,4’-bpp= 4,4’-Trimethylenedipyridine,4,4’-bpt= 3,5-di-（4-pyridyl）-1,2,4-triazoles,4,4’-bpy= 4,4’-bipyridine,2,2’-bpy= 2,2’-bipyridine） have been successfully prepared. Structure analyses demonstrate that both compounds 5 and 6 exhibit 3D frameworks consisted of trinuclear Cd unit, in which H₃TCA presents three bridged fashions; Compound 7 displays 3D framework consisted of mononuclear Cd unit while H₃TCA presents single bridged fashion; There are three Cd ions in the asymmetric unit of compound 8, Cd ions are linked to each other to form a 3D framework with bridges of H₃TCA and ancillary ligand. The researches show that compounds 5 and 8 display high selectivity for Fe³⁺ ion, and compounds 6 and 7 provide an ideal luminescence sensor for high selective probing Pb²⁺/Cu²⁺ ions and Na⁺/Fe³⁺ ions, respectively.更多还原