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研究生： 謝武憲
Sie, Wu-Sian
論文名稱： 三價銥錯合物的綠色合成與元件應用之研究
A Study on Green Synthesis and Device Application of Iridium (III) Complexes
指導教授： 許拱北
Shiu, Kom-Bei
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 218
中文關鍵詞： 銥 、自組裝 、有機發光二極體 、研磨合成 、水熱法 、機械化學
外文關鍵詞： iridium, OLED, LEC, Green chemistry, hydrothermal synthesis
相關次數： 點閱：103  下載：0 
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    • 本論文利用自組裝合成的方式以[Ir(2-ppy)2(MeCN)2][NO3] (S1) 與[Ir(2-tpy)2(MeCN)2][NO3] (S2)做為起始物(ppy = 2-phenylpyridine、 tpy = 2-(p-tolyl)pyridine)，順利的合成出2個四核環狀銥(III)金屬化合物[Ir(2-ppy)2(-4,4’-bp)]4(NO3)4 (1a)、 [Ir(2-tpy)2(-4,4’-bp)]4 (NO3)4 (2a) 與2個二核環狀銥金屬化合物[Ir(2-ppy)2(-1,2-dpe)]2 (NO3)2 (1b)、[Ir(2-tpy)2(-1,2-dpe)]2(NO3)2 (2b)，另外並合成一個單核銥金屬化合物[Ir(2-ppy)2(py)2](NO3) (3a) 作為性質上的比較(4,4’-bp = 4,4’-bipyridine、 1,2-dpe = 1,2-di(4-pyridyl)ethane、 py = pyridine)，所有的化合物均利用元素分析、IR及NMR光譜進行鑑定，其中1a、2a、2b與3a也進一步的得到單晶結構，所得到的產物的光物理性質也有進行研究，並進一步的應用在OLED與LEC元件的發光層上。
    另一部份，利用研磨法與水熱法的合成方式，將一系列銥(III)化合物以無溶劑或是水溶劑進行合成，改良原本文獻使用有機溶劑的作法，使該系列化合物的合成更符合綠色化學的精神，也將產率提高、時間縮短，讓合成更有效率。
    利用研磨的方式可以順利合成出[M(2-N^C)2(MeCN)2](NO3)、[M(2-(N^C)2(-X)]2、[M(2-N^C)2(2-O^O)]、[M(2-N^C)2(2-O^N)]、[M(2-N^C)2(2-S^S)]、[M(2-N^C)2(2-S^N)]與[M(2-N^C)2(2-N^N)] (NO3)七種類型的化合物，其中 M=Ir、Rh，N^C = ppy、tpy、dfppy，X = Cl、Br、I、SCN，O^O = acac、R-CO2、O^N = pic、hp、hcp，S^S = Et2NCS2、S^N = tp，N^N = 2,2’-bp、phen，(dfppy = 2-(2,4-difluorophenyl)pyridine、acac = acetylacetate、pic = picolate、hp = pyridin-2olate、hcp = 6-chloropyridin-2olate、tp = pyridine-2-thiol、2,2’-bp = 2,2’-bipyridine、phen = 1,10-phenanthroline)，研磨的過程只需要20~40分鐘，產率可以高達90~98%，提供這一系列的化合物一個利用固態研磨且高產率、有效率的新合成方法。
    水熱法的合成方式則是以水當溶劑，利用水熱法的裝置可以順利的以IrCl3為起始物合成出[Ir(2-N^C)2(-X)]2，其中N^C = ppy、tpy與dfppy，X = Cl與I，也可以以[Ir(2-N^C)2(-I)]2 或IrCl3為起始合成出 mer-Ir(2-N^C)3與 fac-Ir(2-N^C)3兩個立體異構物，另外也以[Ir(2-ppy)2(-I)]2為起始物，利用水熱法合成出Ir(2-ppy)2(-L^X)與[Ir(2-ppy)2(2-N^N)](I)，其中L^X = pic、8-hydroxyquinolinm與acac，N^N = 2,2’-bp與phen，藉由調控反應條件，可以利用水當溶劑，以一鍋法的方式便合成出這些化合物，並提高產率，在反應的過程中可減少有機溶劑的使用，利用水熱法合成的方式，我們提供此類型化物一個綠色且有效率的合成新方式。

    In this thesis, we synthesized the cyclo-tetrairidium(III) complexes [Ir(2-ppy)2(-4,4’-bp)]4(NO3)4 (1a), [Ir(2-tpy)2(-4,4’-bp)]4(NO3)4 (2a) and the cyclo-diiridium(III) complexes [Ir(2-ppy)2(-1,2-dpe)]2(NO3)2 (1b), [Ir(2-tpy)2(-1,2-dpe)]2(NO3)2 (2b) by self-assembly approach using the [Ir(2-ppy)2(MeCN)2](NO3) (S1) and [Ir(2-tpy)2(MeCN)2] (NO3) (S2) as the starting material. In addition, we also synthesized the mono-iridium(III) complex [Ir(2-ppy)2(py)2](NO3) (3a) as the properties comparison, where the ppy is 2-phenylpyridine, the 4,4’-bp is 4,4’-bipyridine, the 1,2-dpe is 1,2-di(4-pyridyl)ethane, the tpy is 2-(p-tolyl)pyridine. All the complexes were characterized by element analysis, IR and NMR. The single crystal structure of complexes 1a, 2a, 2b and 3a have been determined. The photo-physical properties of all the complexes are also studied, and further applications in the light-emitting layer of OLED and LEC devices
    Another part, the grinding and hydrothermal synthesis method had been used to synthesis a series of iridium(III) compounds without solvent or using water as the solvent. We modified the original synthesis of literature usage of organic solvents to make the synthesis fit in the spirit of Green Chemistry. We also improve the yields and reduce the time to let the synthesis more efficient.
    Using the grinding method, We can synthesize the seven types of complexes [M(2-N^C)2(MeCN)2](NO3), [M(2-(N^C)2(-X)]2, [M(2-N^C)2(2-O^O)], [M(2-N^C)2(2-O^N)], [M(2-N^C)2(2-S^S)], [M(2-N^C)2(2-S^N)] and [M(2-N^C)2(2-N^N)] (NO3), M = Ir, Rh; N^C = ppy, tpy, dfppy; X = Cl, Br, I, SCN; O^O = acac, R-CO2; O^N = pic, hp, hcp; S^S = Et2NCS2; S^N = tp; N^N = 2,2’-bp, phen. The process of grinding just need 20~40 minutes and the yields can improve up to 90~99 %, where the dfppy is 2-(2,4-difluorophenyl) -pyridine, the acac is acetylacetate, the pic is picolate, the hp is pyridin-2olate, the hcp is 6-chloropyridin-2olate, the tp is pyridine-2-thiol, the 2,2’-bp is 2,2’-bipyridine, the phen is 1,10-phenanthroline. We provide this series of complexes in a new, solid-state grinding, higher yield, and more efficient synthesis method.
    Hydrothermal synthesis is based on water solvent. We use IrCl3 as starting material to synthesize the [Ir(2-N^C)2(-X)]2, where N^C = ppy, tpy and dfppy, X = Cl and I, and use [Ir(2-N^C)2(-I)]2 or IrCl3 as starting material to synthesize the mer-Ir(2-N^C)3 and fac-Ir(2-N^C)3. We also use [Ir(2-ppy)2(-I)]2 as starting material to synthesize the Ir(2-ppy)2(-L^X) and [Ir(2-ppy)2(2-N^N)](I) by hydrothermal synthesis, where L^X = pic, 8-hydroxyquinolinm and acac, N^N = 2,2’-bp and phen. Through the regulation of reaction conditions, we can use water as solvent for one-pot approach to synthesize these series of compounds with improment of yield and reduce the useage of organic solvents. By hydrothermal synthesis, we provide this type of compound a new, green and more efficient way of synthesis.

    目錄 摘要 I Abstract III 誌謝 V 縮寫對照表 VI 目錄 VII 表目錄 IX 圖目錄 XI Section 1 自組裝合成多核環狀銥(III)化合物與元件的應用與討論 1 1-1 序論 1 1-1-1 有機發光二極體OLED簡介 1 1-1-2 電化學發光電池LEC簡介 6 1-1-3螢光材料與磷光材料 9 1-1-4 含金屬自組裝環狀化合物 12 1-1-6 研究動機 16 1-2 實驗部份 20 1-2-1 實驗與儀器操作 20 1-2-2 實驗藥品 23 1-2-3 實驗儀器/軟體 23 1-2-4 實驗合成 25 1-3 結果與討論 32 1-3-1 晶體結構 32 1-3-2 光物理性質 45 1-3-3 OLED元件的放光性質 48 1-3-4 LEC元件的放光性質 52 1-4 結論 56 Section 2 銥與銠化合物的研磨合成 58 2-1 序論 58 2-1-1 綠色化學 58 2-1-2機械化學 62 2-1-3 各種常見的發光材料Ir與Rh錯合物的文獻合成 66 2-1-4 研究動機 69 2-2 實驗部份 71 2-2-1 實驗與儀器操作 71 2-2-2 實驗藥品 71 2-2-3 實驗儀器/軟體 73 2-2-4 實驗合成 73 2-3 結果與討論 89 2-3-1 [M(2-N^C)2(MeCN)2](NO3) (S1~S4)的結果與討論 89 2-3-2 [M(2-(N^C)2(-X)]2 (1~7) 的結果與討論 90 2-3-3 [M(2-N^C)2(2-O^O)] (8~14) 的結果與討論 92 2-3-4 [M(2-N^C)2(2-O^N)] (15~18) 的結果與討論 94 2-3-5 [M(2-N^C)2(2-S^S)] (19~20) 的結果與討論 97 2-3-6 [M(2-N^C)2(2-S^N)] (21) 的結果與討論 98 2-3-7 [M(2-N^C)2(2-N^N)](NO3) (22~24) 的結果與討論 99 2-4 結論 101 Section 3 銥化合物的水熱法合成 102 3-1 序論 102 3-1-1 水熱法簡介 102 3-1-2 Ir(2-N^C)3的文獻合成 105 3-1-3 實驗動機 106 3-2 實驗部份 108 3-2-1實驗與儀器操作 108 3-2-2 實驗藥品 108 3-2-3 實驗儀器/軟體 108 3-2-4 實驗合成 109 3-3 結果與討論 130 3-3-1 [Ir(2-N^C)2(-Cl)]2 的水熱合成 130 3-3-2 [Ir(2-N^C)2(-I)]2 的水熱合成 133 3-3-3 Ir(2-N^C)3 的水熱合成 136 3-3-4 [Ir(2-ppy)2(2-L^X)]的水熱合成 159 3-3-5 [Ir(2-ppy)2(2-N^N)](I)的水熱合成 163 3-4 結論 164 參考文獻 167 附錄 172

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