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N/S杂环配合材料的表证及其荧光性能与离子识别效应

Luminescent Materials and Its Ion-Recognition Effects Based on the N/S Heterocyclic Carboxylic Acid

【作者】 孟彩霞

【导师】 李东升;

【作者基本信息】 延安大学 , 分析化学, 2010, 硕士

【摘要】 利用分析科学的优势去解决其他学科研究中的科学问题是学科交叉融合的一种必然趋势。金属-有机配合材料因其兼有有机和无机材料的特点,加之,可通过引入不同的有机构件对材料的结构和性能进行剪裁来获取目标材料,因此,其设计合成及性能与应用备受关注。本文以含N/S杂环的有机分子为结构基块,d/p区金属离子为中心,采用水热或溶剂热法合成了12个金属-有机配合材料,运用现代分析测试技术,表证了材料的晶体结构、红外光谱特性和热稳定性,重点研究了材料的荧光性能、离子识别效应和构效关系。本文的工作概述如下:1.第一章对金属有机配合材料的基本概念及研究进展进行了概述,重点探讨了配合材料在识别和荧光性质领域的应用,并在此基础上,阐述了本论文的选题依据、重点和意义。2.第二章利用噻吩杂环羧酸配体合成了3个金属有机配合材料,它们是零维配合材料[Zn(Tma)(bpy)(H2O)]·2H2O (1)、一维/二维挂臂式配合材料[Co3(Taa)4(bpy)4]·2ClO4·bpy·2H2O (2)和[Cd(Taa)2(dpp)(H2O)]n (3);对其晶体结构特点、以及热稳定性、红外、荧光等性质进行了研究;在此基础上,考察了配合材料2和3对过渡金属离子的识别效应,发现2对Ag+有良好的识别作用。3.第三章设计合成了一系列咪唑二酸基金属有机配合材料:具有螺旋结构的二维或三维配合材料[Cd(H2pimdc)2]n (4)、[Cd2(Hpimdc)2(bpp)(H2O)]n (5)和[Cd2(Hpimdc)2(bbi)0.5(H2O)2]n (6),二维层状配合材料[Pb(H2pimdc)2(H2O)2]n (7)和一维链状配合材料[Zn(Hpimdc)(H2O)]n (8),对其晶体结构、热稳定性和红外光谱等进行了表征,重点对其荧光性能进行了研究。4.第四章通过含N杂环的有机分子构筑了4个配合材料:具有螺旋结构的二维或三维配合材料[Cd(bbi)2Cl2]n (9)和[Cu(btb)2(H2O)2]·2NO3 (11),三维嵌入式配合材料[Cd2(Naphdc)2(bbi)(H2O)]n (10)和二维挂臂式配合材料[Cu(btdc)2)]n·H2O (12)。对其进行了晶体结构,热稳定性和红外光谱等进行了表证,同时对9和10的荧光光谱进行了解析。5.第五章对本文的工作进行了总结与展望。[H3pimdc=2-丙基-4,5-咪唑二酸,H2Tma=3-噻吩丙二酸,Htaa=3-噻吩乙酸,H2Naphdc= 1,4-萘二酸,H2btdc=苯甲基三唑-4,5-二酸,bbi=1,4-双咪唑丁烷,dpp=1,3-吡啶丙烷,bpy=联吡啶, btb=1,4-双三唑丁烷]

【Abstract】 It is an inevitable trend to analysis of the advantages, which the use of scientific research in other disciplines to solve scientific problems is the interdisciplinary integration. In recent years, the application of coordination materials with kinds of properties has been more active, this trend is justified by the advantages of both inorganic and organic optical materials. In the thesis, tweleve coordination materials based on nitrogen- or sulfur- heterocyclic ligands were designed and constructed by hydrothermal methods. The works are summarized as follows:Firstly, over view of the functional materials of the basic profiles, the research progress on the wrap-up. As well as elaborated the application in luminescence and recognition.Secondly, with 3-thiophene carboxylic acid ligands synthesized three coordination polymer materials, [Zn(Tma)(bpy)(H2O)]·2H2O(1), [Co3(Taa)4(bpy)4]·2ClO4·bpy·2H2O (2), [Cd(Taa)2(dpp)(H2O)]n (3), such as its crystal structure and fluorescence properties were analyzed. On this basis, we mensurated the ion-recognition of functional materials 2 and 3, found that 2 have a good recognition effect for Ag +. Thirdly, five metal–organic materials based on 2-propgl-1H-imidazole4,5-dicarboxy Acid (H3pimdc) had synthesized and studied: [Cd(H2pimdc)2]n (4), [Cd2(Hpimdc)2(bpp)(H2O)]n (5), [Cd2(Hpimdc)2(bbi)0.5(H2O)2]n (6), [Pb(H2pimdc)2(H2O)2]n (7), [Zn(Hpimdc)(H2O)]n (8). We have investigated their IR, TG and fluorescence properties.Fourthly, we select another nitrogen- heterocyclic complex as the basic building units, assembly synthesized 4 new functional materials: two-dimensional or three-dimensional materials with many different helical structure: [Cd(bbi)2Cl2]n (9), [Cu(btb)2(H2O)2]·2NO3 (11), three-dimensional embedded coordinate materials [Cd2(Naphdc)2(bbi)(H2O)]n (10), two-dimensional materials with hanging arm: [Cu(btdc)2)]n·H2O (12), investigated their Crystal structures, IR, TG and fluorescence properties.Finally, conclude a brief summary and viewed the outlook of this work. [H2Tma=3-thiophenemalonic Acid, Htaa=thiophene-3-acetic acid, H3pimdc=2-propgl-1H-imidazole4,5-dicarboxy Acid, H2Naphdc= Naphthalene-1,4-dicarboxylic acid, H2btdc=1-Benzyl-1,2,3-triazole-4,5-dicarboxylic acid, bbi=1,1′-(1,4-butanediyl)bis(imidaz-ole), dpp=1,3-Di(4-pyridyl)propane, btb=1,4-Bis(triazol)butane, bpy=bipyridine ]

  • 【网络出版投稿人】 延安大学
  • 【网络出版年期】2011年 05期
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