Synthesis,Structures and Luminescence Sensing Properties of Europium(Ⅲ) and Terbium(Ⅲ) Metal-Organic Coordination Polymers

摘要

金属有机配位聚合物是由有机桥联配体和金属离子或者金属簇通过配位键或者超分子相互作用自组装构成的周期性网络结构。与过渡金属配位聚合物相比，发光稀土金属配位聚合物具有色纯度高、发射峰窄和发光寿命长等特点，在荧光传感、电致发光、生物成像等领域展现潜在应用前景。然而，由于很多被分析物强的电子亲和性和吸附能力，高选择性和灵敏性检测痕量金属离子和硝基芳香化合物仍然是很大的挑战。本论文设计合成了一系列一维、二维、三维Eu(Ⅲ)和Tb(Ⅲ)配位聚合物。研究了其单晶结构和光致发光性质，研究了其用于金属离子和硝基芳香化合物的选择性检测，揭示了其发光传感机理;制备了具有选择性识别功能的发光试纸。论文主要内容如下:
　　(1)红色发光Eu(Ⅲ)配位聚合物的合成、结构及选择性检测4-硝基苯酚(4-NP)和三价铁离子(Fe3+)。在水热/溶剂热条件下，利用Eu(Ⅲ)离子与均苯四甲酸和对联苯二甲酸组装，分别合成了两种Eu(Ⅲ)配位聚合物。[Eu(H2O)5(BTEC)2]·[H(C5H6N2)]·3H2O(1)具有带负电荷的zig-zag链结构;[Eu(BPDC)2]·(CH3)2NH2(2)具有三维阴离子骨架结构，质子化的[(CH3]2(NH2)]+作为客体分子存在其孔道中。化合物1和2在593-691nm范围展现了Eu3+特征发射，其红色荧光可以被痕量Fe3+或者4-NP猝灭，然而对其他金属离子和硝基化合物没有明显的荧光猝灭。通过热失重、XRD、发光寿命等研究了其荧光猝灭机理。
　　(2)绿色发光Tb(Ⅲ)配位聚合物的合成、结构及选择性检测4-NP和Fe3+。在水热条件下，通过Tb(Ⅲ)和均苯四甲酸及辅助配体4-氨基咪唑自组装合成了Tb(BTEC)0.5(HCOO)(H2O)2(3)和[Tb(H2O)5(BTEC)]·[H(C5H6N2)]·3H2O(4)。化合物3具有由二聚体构筑块形成的二维蜂窝结构。化合物4具有一维羧酸基团功能位点修饰的zig-zag阴离子链结构，并且层间通道内含有质子化的4-氨基咪唑客体分子。化合物3和4在489-620 nm范围内具有Tb(Ⅲ)的5D4→7FJ(J=6，5，4，3)特征跃迁发射。两个化合物强的绿色荧光可用于定性和定量测定Fe3+和4-NP烃化合物。即使在相似物存在条件下，二者的传感性质也不被影响;通过紫外吸收光谱、XRD、发光寿命等研究了其传感检测机理。
　　(3)双通道检测铀酰离子(UO22+)的绿色发光Tb(Ⅲ)金属有机配位聚合物。溶剂热反应条件下，利用对联苯二甲酸和Tb(NO3)3·6H2O在水/DMF混合溶剂中反应，合成了Tb(Ⅲ)金属配位聚合物[Tb(BPDC)2]·(CH3)2NH2(5)。5是具有三维骨架的阴离子，质子化的二甲胺分子被包埋在孔道结构中。化合物5是首个能够检测水相中UO22+的高效双通道发光传感分子。即使在其他竞争性的金属离子的存在条件下，化合物5的荧光依然能够被UO22+高选择性和高灵敏度的猝灭。研究了化合物5、6荧光共振能量转移抑制和分子间电子转移增强的协同传感检测机理。
　　(4)可视化检测金属离子和硝基化合物的的红色、绿色荧光检测试纸。基于化合物1、3、4、5分别制备了红色荧光和绿色荧光试纸，并可用于检测水中Fe3+和4-NP。对于检测4-NP的试纸经过7次浸泡-洗涤循环之后，试纸仍然显示出很强的红色发射强度。然而检测Fe3+的试纸发射强度没有恢复到初始强度。化合物5制备的绿色测试试纸可以选择性检测水中UO22+。

目录

声明

Abstract

摘要

CONTENTS

List of compounds in this thesis

List of Tables

List of Figures

1 Introduction

1．1 Brief Background of Metal-organic Coordination Polymers

1．1．1 Design

1．1．2 Synthesis

1．1．3 Secondary Building units(SBUs)in metal organic frameworks

1．1．4 Dimensionality

1．1．5 Potential Applications of Metal organic Coordination Polymers

1．2 Recent research progress on luminescent metal organic coordination polymers

1．3 Luminescence phenomena of metal-organic coordination polymers

1．4 Luminescence sensing mechanism of metal organic coordination polymers

1．5 Lanthanide coordination polymers

1．6 Lanthanide metal organic frameworks as sensors

1．6．1 Sensing metal ions

1．6．2 Sensing nitroaromatic compounds

1．7 Motivation，Significance and Design of this Thesis

2 Red luminescence of europium(Ⅲ)coordination polymers and their sensing towards 4-nitrophenol and Fe3+ion

2．1 Introduction

2．2 Experimental Section

2．2．2 Synthesis of [Eu(H2O)5(BTEC)2]·[H(C5H6N2)]·3H2O(1)

2．2．4 X-ray crystallography

2．2．5 Luminescent measurements

2．3 Structural characterization of Eu-based coordination polymers 1 and 2

2．3．1 Structure determination of compound 1

2．3．2 Structure determination of compound 2

2．4 Luminescent properties of Eu-coordination polymers 1 and 2

2．5 Eu-based coordination polymers as sensors for metal ions and nitroaromaatics(NACs)

2．5．1 Sensing metal ions

2．5．2 Sensing nitroaromatic compounds

2．6 Possible sensing mechanisms of compounds 1 and 2 towards 4-nitrophenl and Fe3+ion

2．7 Luminescent test papers based on compounds 1 and 2

2．8 Brief Summary

3 Green Luminescence of Terbium(Ⅲ) Coordination Polymers and their sensing towards 4-nitrophenol and Fe3+ion

3．1 Introduction

3．2 Experimental Section

3．2．1 Materials and Methods

3．2．2 Synthesis of Tb(BTEC)0．5(HCOO)(H2O)2(3)

3．2．5 Luminescent measurements

3．3 Structural Characterization of Tb-based coordination polymers 3 and 4

3．3．1 Structure determination of compound 3

3．3．2 Structure determination of compound 4

3．4 Luminescent Properties of Tb-Coordination Polymers 3 and 4

3．5 Tb-based coordination polymers as sensors for metal ions and nitroaromaatics(NACs)

3．5．1 sensing nitroaromatic compounds

3．5．2 sensing metal ions

3．6 Possible Sensing Mechanisms based on Compounds 3 and 4

3．6．1 Sensing of Compound 3 Towards 4-nitrophenol and Fe3+

3．6．2 Sensing of Compound 4 Towards 4-nitrophenol and Fe3+ ion

3．7 Luminescent test papers based on compounds 3 and 4

3．8 Brief Summary

4 A water stable dual-channel luminescence sensor for UO22+ion based on an anionic terbium(Ⅲ)metal-organic framework

4．1 Introduction

4．2 Experimental Section

4．2．1 Materials and general methods

4．2．2 Synthesis of [Tb(BPDC)2]·(CH3)2NH2(5)

4．2．3 Single-crystal structure determination

4．2．4 Luminescent measurements

4．3 Structural characterization of compound 5

4．3．1 Structure Determination of compound 5

4．4 Luminescent properties of compound 5

4．5 Sensing properties of compound 5 towards to UO22+ion

4．6 Possible sensing mechanism of compound 5 towards UO22+ion

4．7 Luminescent test papers based on compound 5

4．8 Brief Summary

5 Conclusions and Outlook

5．1 Summary

5．2 Abstract of Innovation Points

5．3．Outlook

References

Published Academic Thesis during PhD Period

Acknowledgement

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