咔唑双酮类配合物合成表征与光电性质研究
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摘要
本论文在大量文献调研的基础上，对β-二酮的结构特点和研究状况、稀土配合物发光材料和多吡啶钌(Ⅱ)配合物光电性质研究进展进行了较详细的综述。在发光材料方面，铕的配合物以其独特的发光特性使其在电致发光材料方面具有诱人的应用前景。多吡啶钌(Ⅱ)配合物在光化学、光物理、光电化学、电化学、电子转移和能量传递、分子识别和分子组装等研究领域都扮演着重要的角色，其中对它们进行电子转移、能量传递和非线性光学性质的研究很有意义。我们通过分子设计，将合成的双β-二酮有机配体与铕和钌(Ⅱ)多吡啶配位，组装出一系列具有光电功能性质的铕和钌的配合物。主要研究内容如下：
1．合成了两种新型具有光电活性的双β-二酮有机配体L~1[9-丁基-3，6-二(4，4，4-三氟-1，3-丁二酮基)咔唑]、L~2[9-己基-3，6-二(4，4，4-三氟-1，3-丁二酮基)咔唑]和β-二酮有机配体L~3[9-丁基-3-(4，4，4-三氟-1，3-丁二酮基)咔唑]、L~4[9-己基-3-(4，4，4-三氟-1，3-丁二酮基)咔唑]。讨论了双β-二酮化合物的合成条件和反应机理。
2．获得了配体L~1、L~2、L~4的单晶，L~1、L~4晶体属单斜晶系，P2(1)／c空间群，L~2晶体属正交斜晶系，Pbca空间群。都以烯醇式共振结构存在，L~1、L~4咔唑环和双酮环基本共平面，L~2咔唑环和双酮环平面有一定的扭曲。所有分子在空间两维线尺寸都达到纳米级。
3．用一个双β—二酮配体、四个单β—二酮配体与铕组装，得到咔唑桥联双核五咔唑的铕配合物和用一个双β—二酮桥联钌(Ⅱ)联吡啶的配合物。用红外光谱、质谱、元素分析、核磁共振氢谱、X-射线衍射等分析手段确认了所得到目标产物的结构。
4．用电子吸收光谱、单光子液体荧光、光致发光、Z-扫描、双光子荧光、循环伏安、差分脉冲等方法研究了β—二酮配体及其配合物的线性、非线性光学性质和电化学性质等。得到了发光强色纯度高人的眼睛敏感的红光铕的配合物，同时也具有纯正的双光子红色荧光性质。得到的钌(Ⅱ)联吡啶的配合物具有较好的非线性光学性质和好的氧化还原电化学性质。
5．．采用密度泛函理论对配体L~1的电子吸收光谱进行了理论计算。为了解双
Recent progress for β-diketone derivatives were reviewed based on reading a great deal of related literature including Photoluminescence (PL) and Electroluminescence ( EL) of rear earth metal complexes and the photoelectric properties of multi-pyridine Ru(II) complexes. The europium complexes have an efficiency high PL, the monochrome red light and so on, making it be EL materials in application. Multi-pyridine Ru(II) complexes have been playing an important role in the research of photochemistry, photophysics, electronchemistry, charge transfer, etc. By molecular designing, we synthesized four novel β-diketone and a series of europium complexes and multi-pyridine Ru(II) complexes. Main research results in this dissertation were summarized as below.
1. Two kinds of new bi-β-diketone of the PL & EL active organic ligand L~1 (3,6-bis(4,4,4-trifluorobutane-1,3-dione)-9-butylcarbazole) , L~2 (3,6-bis(4,4,4-tri
fluorobutane-1,3-dione)-9-hexylcarbazole ) and two kinds of new β-ditone L~3 (3-(4,4,4- trifluorobutane-1,3-dione)-9-butylcarbazole), L~4 (3-(4,4,4-trifluorobutane -1,3-dione)-9-hexylcarbazole) were synthesized and their synthetic conditions and the reaction mechanisms were also discussed.
2. Single crystals for the three organic ligands L~1, L~2, L~4 were obtained, in which L~1, L~4 belong to monoclinic system, P2_1/c space group, while L~2 belong to orthorhombic system, Pbca space group. The ligands exhibit in enol-form resonance The carbazole and the diketone groups in L~1 and L~4 are almost in one plane while those in L~2 exhibit slight twist. The size for the three kinds of the molecules reach to nano-scale.
3. A series of multi-pyridine Ru(II) and europium complexes of the ligands were obtained, which were characterized by IR spectra, ~1H NMR, MS, elemental analysis and X-ray diffiraction analysis. The structural characters for them were studied in detail.
1．合成了两种新型具有光电活性的双β-二酮有机配体L~1[9-丁基-3，6-二(4，4，4-三氟-1，3-丁二酮基)咔唑]、L~2[9-己基-3，6-二(4，4，4-三氟-1，3-丁二酮基)咔唑]和β-二酮有机配体L~3[9-丁基-3-(4，4，4-三氟-1，3-丁二酮基)咔唑]、L~4[9-己基-3-(4，4，4-三氟-1，3-丁二酮基)咔唑]。讨论了双β-二酮化合物的合成条件和反应机理。
2．获得了配体L~1、L~2、L~4的单晶，L~1、L~4晶体属单斜晶系，P2(1)／c空间群，L~2晶体属正交斜晶系，Pbca空间群。都以烯醇式共振结构存在，L~1、L~4咔唑环和双酮环基本共平面，L~2咔唑环和双酮环平面有一定的扭曲。所有分子在空间两维线尺寸都达到纳米级。
3．用一个双β—二酮配体、四个单β—二酮配体与铕组装，得到咔唑桥联双核五咔唑的铕配合物和用一个双β—二酮桥联钌(Ⅱ)联吡啶的配合物。用红外光谱、质谱、元素分析、核磁共振氢谱、X-射线衍射等分析手段确认了所得到目标产物的结构。
4．用电子吸收光谱、单光子液体荧光、光致发光、Z-扫描、双光子荧光、循环伏安、差分脉冲等方法研究了β—二酮配体及其配合物的线性、非线性光学性质和电化学性质等。得到了发光强色纯度高人的眼睛敏感的红光铕的配合物，同时也具有纯正的双光子红色荧光性质。得到的钌(Ⅱ)联吡啶的配合物具有较好的非线性光学性质和好的氧化还原电化学性质。
5．．采用密度泛函理论对配体L~1的电子吸收光谱进行了理论计算。为了解双
Recent progress for β-diketone derivatives were reviewed based on reading a great deal of related literature including Photoluminescence (PL) and Electroluminescence ( EL) of rear earth metal complexes and the photoelectric properties of multi-pyridine Ru(II) complexes. The europium complexes have an efficiency high PL, the monochrome red light and so on, making it be EL materials in application. Multi-pyridine Ru(II) complexes have been playing an important role in the research of photochemistry, photophysics, electronchemistry, charge transfer, etc. By molecular designing, we synthesized four novel β-diketone and a series of europium complexes and multi-pyridine Ru(II) complexes. Main research results in this dissertation were summarized as below.
1. Two kinds of new bi-β-diketone of the PL & EL active organic ligand L~1 (3,6-bis(4,4,4-trifluorobutane-1,3-dione)-9-butylcarbazole) , L~2 (3,6-bis(4,4,4-tri
fluorobutane-1,3-dione)-9-hexylcarbazole ) and two kinds of new β-ditone L~3 (3-(4,4,4- trifluorobutane-1,3-dione)-9-butylcarbazole), L~4 (3-(4,4,4-trifluorobutane -1,3-dione)-9-hexylcarbazole) were synthesized and their synthetic conditions and the reaction mechanisms were also discussed.
2. Single crystals for the three organic ligands L~1, L~2, L~4 were obtained, in which L~1, L~4 belong to monoclinic system, P2_1/c space group, while L~2 belong to orthorhombic system, Pbca space group. The ligands exhibit in enol-form resonance The carbazole and the diketone groups in L~1 and L~4 are almost in one plane while those in L~2 exhibit slight twist. The size for the three kinds of the molecules reach to nano-scale.
3. A series of multi-pyridine Ru(II) and europium complexes of the ligands were obtained, which were characterized by IR spectra, ~1H NMR, MS, elemental analysis and X-ray diffiraction analysis. The structural characters for them were studied in detail.
引文
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