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类型 基础研究 预答辩日期 2018-05-15
开始(开题)日期 2016-05-25 论文结束日期 2018-03-28
地点 化工老楼319会议室 论文选题来源 其他项目    论文字数 8 (万字)
题目 基于半刚性芳羧酸配体构建的MOFs材料的设计,合成,结构及功能性研究
主题词 金属-有机框架材料,荧光探针,硝基高爆物,光催化,半刚性
摘要 本论文采用两个半刚性芳羧酸配体4,4’-二羧基-4’’-硝基三苯胺(H2L)、4-(羧甲氧基)-[1,1’-联苯]-3,4’-二羧酸(H3Lws)与不同金属离子,通过水热或溶剂法得到22个金属-有机框架材料(MOFs),并对它们的合成,结构及性质进行了详细的研究与讨论。主要分为以下四部分内容: (1)基于半刚性H2L配体与d10过渡金属离子构筑的MOFs:[Zn(L)(4,4’-bpy)0.5(H2O)]0.25 (1),[Cd4(L)4(4,4’-bpy)] 2(H2O) (2)和[Zn4(L)4(4,4’-bpy)(H2O)2].2H2O.2CH3CN (3)。配合物1是一例基于一维珠串链的二维层状结构,而配合物2为二重穿插的三维网络结构。基于荧光淬灭效应,配合物1和2具有水相中检测硫化氢分子的能力,检测限分别为7.9 μM和0.2 μM。配合物3是一例罕见的内含八面体笼的二维层状结构,在DMAc体系中3具有荧光识别Fe3+离子的能力。 (2)基于半刚性H2L配体与单d电子过渡金属离子构筑的MOFs:[Cu(L)(H2O)].(CH3CN)0.25] (4),[Co4(L)4(4,4’-bpy)(H2O)2].2H2O (5)和[Co(L)(Phen) (6)。配合物4是一例结构稀有的三维多孔材料,结构中含有左旋和右旋螺旋链形成的二重穿插层状平面,具有较好的耐酸碱性能。磁性研究发现,4中相邻铜离子间呈较强的反铁磁耦合作用。此外,配合物4具有可见光催化降解有机染料分子(结晶紫、刚果红、罗丹明6G和藏红T)和催化氧化苯硼酸及其衍生物偶联反应的双重性能。配合物5是一例基于八面体笼的二维层状结构,配合物6是一维“之”字链结构,两个配合物均具有较好的热稳定性和水解稳定性。 (3)基于半刚性H2L配体与镧系金属离子构筑的MOFs:[La(L)(H2O)].(CH3CN)0.25] (7),[La2(L)3(H2O)4].(CH3CN)3.H2O (8),[Nd2(L)3(H2O)4].H2O (9),Tb2(L)3(H2O)3.(CH3CN)(H2O)1.5 (10),Eu2(L)3(H2O)3.(CH3CN)2(H2O) (11),Sm2(L)3(H2O)3.(CH3CN) (12),Dy2(L)3(H2O)3.(CH3CN)(H2O) (13),Yb2(L)3.(H2O)1.5 (14),[Ce2(L)3(H2O)4].CH3CN (15),[Pr2(L)3(H2O)4]. (CH3CN)4 (16),Er2(L)3.(CH3CN) (17)。配合物7(La)是一例由二维层状结构堆叠形成的三维多孔材料,可用于荧光识别Fe3+和Cu2+离子。配合物8(La’)、9(Nd)、15(Ce)和16(Pr)是具有相同拓扑类型(raz2)的三维多孔材料。其中,配合物8(La’)和9(Nd) 9具有荧光识别Fe3+的能力。配合物10(Tb)、11(Eu)、12(Sm)和13(Dy)同构,是由棒状金属链和有机配体连接形成的三维多孔结构。其中,配合物10(Tb)具有荧光识别Fe3+和Cu2+的能力,配合物11(Eu)和12(Sm)具有检测苄醇中苯甲醛含量的能力,配合物13(Dy)具有检测含酚羟基硝基高爆物的能力。配合物14(Yb)和17(Er)的结构有点相似,金属离子均采去五角双锥的几何构型与配体连接,最终形成含三种孔道的三维网络结构,其中配合物14(Yb)可以作为NACs的荧光探针,尤其对含酚羟基类的NACs具有较高的识别能力。 (4)基于水杨酸衍生物配体H3Lws和H2bsal与过渡金属离子的MOFs:Co(HLws)](H2O)2 (18),Ni2(Lws)(OH)(H2O)3 (19),Cd2(Lws)(OH) (20),Cu(Hbsal)2(4,4’-bpy)2(21)和Cu(Hbsal)(4,4’-bpy)(22)。配合物18和19分别为一维链状和二维层状结构,二者结构中存在大量的氢键,极大地提高了配合物的水解稳定性。配合物20是一例三维非穿插的网络结构,具有水相中荧光识别NACs的能力,尤其对2,4-DNP,TNP和PNP)具有较高的选择性。配合物21和22分别为一维线性链和三维多孔sod拓扑结构。有趣的是,配合物21在DMF溶剂中浸泡后,可以自发地以固态的形式转变为配合物22,同时伴随有颜色和磁性的明显变化。
英文题目 Metal-Organic Frameworks Based on Semi-Rigid Aromatic Carboxylate: Syntheses, Structures and Functions
英文主题词 Metal-organic frameworks, Fluorescent probe, Nitro-aromatic compounds, Photocatalysis, Semi-rigid ligand
英文摘要 In the dissertation, twenty-two new metal-organic frameworks (MOFs) have been successfully constructed based on two semi-rigid aromatic carboxylic acids, viz. 4,4’-dicarboxy-4’’-nitrotriphenylamine(H2L) and 4-(carboxymethoxy)-[1,1’-biphenyl]-3,4’-di- carboxylic acid (H3Lws), under hydrothermal or solvothermal conditions. Syntheses, structures and properties of these complexes have been investigated and discussed in detail and the main work of this dissertation includes the following four parts: (1) MOFs based on H2L ligand and Zn2+, Cd2+ ions: [Zn(L)(4,4’-bpy)0.5(H2O)]0.25 (1), [Cd4(L)4(4,4’-bpy)] 2(H2O) (2) and [Zn4(L)4(4,4’-bpy)(H2O)2].2H2O.2CH3CN (3). Complexes 1 and 3 are two 2-D layered structures based on 1-D beaded chains, and complex 2 exhibits a two-fold interpenetrating 3-D network. Complexes can serve as a highly sensitive and selective fluorescence sensor for aqueous detection of hydrogen sulfide, and the detection limit of 1 and 2 was 7.9 μM and 0.2 μM, respectively. Complex 3 has the ability to detect Fe3+ ion in DMAc solvent. (2) Three MOFs based on H2L ligand and Cu2+, Co2+ ions: [Cu(L)(H2O)].(CH3CN)0.25] (4), [Co4(L)4(4,4’-bpy)(H2O)2].2H2O (5) and [Co(L)(Phen) (6). Complex 4 exhibits a 3-D porous network assembled by 2-D two-fold interpenetrating sheet comprising helical chains, and shows outstanding chemical robustness which can withstand acidic or basic aqueous solution as well as various organic solvents. Complex 4 displays a typical antiferromagnetic interaction between adjacent copper ions. In particular, 4 not only displays a notable visible-light photocatalytic activity for degrading oragnic dyes (e.g. crystal violet (CV), rhodamine 6G (R6G), congo red (CR) and basic red 2 (BR2)) with the assistance of H2O2 but also can catalyze the oxidation-coupling reaction of phenylboronic acid and its derivatives. Complex 5 is a 2-D layered structure based on octahedral cage, and the complex 6 exhibits a 1-D zigzag chain with good thermal stability. (3) MOFs based on H2L ligand and lanthanide metal ions: [La(H2L)(H2O)].(CH3CN)0.25] (7), [La2(L)3(H2O)4].(CH3CN)3.H2O (8), [Nd2(L)3(H2O)4].H2O (9), Tb2(L)3(H2O)3.(CH3CN)(H2O)1.5 (10), Eu2(L)3(H2O)3.(CH3CN)2(H2O) (11, Sm2(L)3(H2O)3.(CH3CN) (12), Dy2(L)3(H2O)3.(CH3CN)(H2O) (13), Yb2(L)3.(H2O)1.5 (14), [Ce2(L)3(H2O)4].CH3CN (15), [Pr2(L)3(H2O)4]. (CH3CN)4 (16) and Er2(L)3.(CH3CN) (17). Complex 7 (La) is a 3-D porous MOF constructed by stacking of 2-D layered structures and can be used as a fluorescent probe for detecting Fe3+ and Cu2+ ions. Complexes 8 (La’), 9 (Nd), 15 (Ce) and 16 (Pr) are isomorphic with the raz2 topology. Amongst, 8 (La’) and 9 (Nd) can serve as probes to detect Fe3+ ion. Complexes 10 (Tb), 11 (Eu), 12 (Sm) and 13 (Dy) are also isostructural dispalying 3-D porous structures based on rod-shaped metal chains and bridging ligands. Among them, complex 10 (Tb) has the ability to identify Fe3+ and Cu2+; Complexes 11 (Eu) and 12 (Sm) can act as a fluorescent probe for detecting benzaldehyde in benzyl alcohol solvent. Complexes 13 (Dy) and 14 (Yb) display different luminescence responses toward different NACs with superb sensitivity for 2,4-DNP, TNP and PNP. The structures of 17 (Er) and 14 (Yb) are similar, wherein all metal ions adopt the pentagonal double-cone geometry to connect with the ligand forming a three-dimensional network containing three kinds of channels. (4) MOFs based on H3Lws and H2bsal ligands: Co(HLws)](H2O)2 (18), Ni2(Lws)(OH)(H2O)3 (19), Cd2(Lws)(OH) (20), Cu(Hbsal)2(4,4’-bpy)2 (21) and Cu(Hbsal)(4,4’-bpy) (22). Complexes 18 and 19 are 1-D chain and 2-D layered structures, respectively, and there are a large number of hydrogen bonds in their structures, which greatly improves their hydrolytic stability. Complex 20 is a 3-D non-interpenetrating network, and shows superb sensitivity for NACs especially for 2,4-DNP, TNP and PNP. Complexes 21 is a 1-D linear chain, and 22 is a 3-D porous supermolecular framework with sod topology. What is the most interesting finding is that compound 21 can be irreversibly transformed into 22 in a crystal-to-crystal manner in the case that compound 21 is immersed into DMF solvent. Particularly, the 1D-to-3D crystal-to-crystal structural transformaiton also incurres a drastic change in the magnetic properties of 21 and 22.
学术讨论
主办单位时间地点报告人报告主题
化学化工学院 2015年12月15日 化工院报告厅307室 包如胜高级工程师 化学合成工艺与EHS
诸海滨课题组 2014年12月5日 化工院319会议室 杨旭锋及课题组同学 半刚性羧酸配体(H3Lws)的合成
诸海滨课题组 2015年6月26日 化工院319会议室 杨旭锋及课题组同学 半刚性配体H2L的合成
诸海滨课题组 2016年12月30日 化工院319会议室 杨旭锋及课题组同学 基于H2L的MOFs材料的合成及其硫化氢的检测
诸海滨课题组 2017年3月24日 化工院319会议室 杨旭锋及课题组同学 Tb-MOF对三价铁离子的检测
诸海滨课题组 2017年5月26日 化工院319会议室 杨旭锋及课题组同学 Sm-MOF对苯甲醛的荧光识别
化学化工学院 2017年6月5日 化工院报告厅307室 卢小泉教授 纳米界面的新型可视化传感
诸海滨课题组 2015年3月6日 化工院319会议室 杨旭锋及课题组同学 晶体到晶体的转化研究
     
学术会议
会议名称时间地点本人报告本人报告题目
第九届国际材料先进技术会议 2017年6月18-23日 新加坡 Water-stable transition-metal-based coordination polymers constructed by a polytopic ligand for the aqueous detection of nitroaromatics
中国化学会第九届全国无机化学学术会议 2015年7月25-29日 南昌大学 基于稀土金属MOF的合成,结构及荧光性能的研究
     
代表作
论文名称
Syntheses, structures, and magnetic properties of two unique Cu(II)-based coordination polymers invo
Transition-metal-based (Zn2+ and Cd2+) metal-organic frameworks as fluorescence "turn-off" sensors f
Two unique isomorphic Zn2+ and Co2+-based metal-organic frameworks comprising octahedral cage
Transition-metal-based (Co2+, Ni2+ and Cd2+) coordination polymers constructed by a polytopic ligand
 
答辩委员会组成信息
姓名职称导师类别工作单位是否主席备注
杨锦飞 正高 教授 博导 南京师范大学
许岩 正高 教授 博导 南京工业大学
孙岳明 正高 教授 博导 东南大学
苟少华 正高 教授 博导 东南大学
陈金喜 正高 教授 博导 东南大学
      
答辩秘书信息
姓名职称工作单位备注
徐刚 其他 讲师 东南大学