雙核吡唑基-吡啶錸金屬錯合物之合成、結構鑑定與物性研究

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姓名

李慈玲(Tzu-Ling Lee) 查詢紙本館藏

畢業系所

化學學系

論文名稱

雙核吡唑基-吡啶錸金屬錯合物之合成、結構鑑定與物性研究
(The Synthesis, Characterization, and Physical Properties of Dinuclear Pyrazolyl-pyridine Re(I) Tricarbonyl Complexes)

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摘要(中)

本篇論文以Bppb (1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene) 或BppEb (1,2-bis(2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)ethyl)benzene) 為主結構，錸金屬為配位中心，合成一系列預期與陰離子可產生具陰離子-π作用之錸金屬錯合物，Bppb-Re-R與BppEb-Re-R (R = Br, Ph (4-phenylpyridine), L1 (2-hexyl-7-pyridin-4-yl-benzo[lmn][3,8]phenanthroline-1,3,6,8-tetraone)。
在Bppb系列，Bppb-Re-Ph與Bppb-Re-L1的1H NMR圖譜顯示最靠近吡啶的碳上氫有兩組訊號 (δ = 9.39與9.34 ppm)，表示有兩種結構。利用雙層溶劑擴散法 (acetone/hexane) 得到黃色晶體Bppb-Re-Ph。單晶結構為U型，1H NMR訊號在δ = 9.39 ppm；故推斷訊號在δ = 9.34 ppm的結構為Z型。
Bppb-Re-Ph之U型結構出現1MLCTRe→Bppb的吸收峰 (~360 nm)，放光位置則是在500 nm (在CH2Cl2下量子產率為0.297，放光生命週期為2.34 µs)。
1H NMR圖譜顯示來自BppEb吡啶的碳上氫訊號只有一組，BppEb-Re-Ph的δ = 9.36 ppm，BppEb-Re-L1的δ = 9.40 ppm，參考Bppb系列的1H NMR位置，推論BppEb-Re-Ph的結構為Z型，BppEb-Re-L1的結構為U型。

摘要(英)

A series of dinuclear rhenium(I) tricarbonyl complexes [Bppb-Re-R] and [BppEb-Re-R] (R = Br, Ph (4-phenylpyridine), L1 (2-hexyl-7-pyridin-4-yl-benzo[lmn][3,8]phenanthroline-1,3,6,8-tetraone) containing bidentate 1,3-bis((3-(pyridine-2-yl)-1H-pyrazol-1-yl)methyl)benzene (Bppb) or 1,2-bis(2-(3- (pyridine-2-yl)-1H-pyrazol-1-yl)ethyl)benzene (BppEb) ligand has been designed and synthesized.
The 1H NMR spectra of Bppb-Re-Ph and Bppb-Re-L1 showed distinct signals, indicative of both Bppb-Re-Ph and Bppb-Re-L1 possessing two conformations. The single crystal of Bppb-Re-Ph for X-ray diffraction with U-shaped conformation was grown by diffusing diethyl ether into an acetone solution. The 1H NMR spectrum of the U-shaped isomer showed the signal at δ = 9.39 ppm. Thus, the signal located at δ = 9.34 ppm may be attributed to the conformation isomer of Z form.
The absorption spectrum of Bppb-Re-Ph with U-shaped conformation exhibited broad absorption between 330 and 390 nm with a predominant character of 1MLCTRe→Bppb transition and the emission spectrum displayed at 500 nm. (quantum yield 0.279, lifetime 2.34 µs in CH2Cl2)
Comparing to those of Bppb series, the 1H NMR spectra show that both BppEb-Re-Ph and BppEb-Re-L1 may have only one conformation.

關鍵字(中)

★ 陰離子pi作用
★ 錸金屬

關鍵字(英)

★ Anion pi interaction
★ Rhenium

論文目次

中文摘要 I
英文摘要 III
致謝辭 V
目錄 IX
圖表目錄 XIII
附圖目錄 XVIII
一、緒論 1
1-1 前言 1
1-2 超分子化學 3
1-3 感測器 5
1-3-1 準確性 (Accuracy) 6
1-3-2 選擇性 (Selectivity) 6
1-3-3 可逆性 (Reversibility) 7
1-3-4 靈敏度 (Sensitivity) 7
1-4 偵測陰離子之困難度 8
1-4-1 幾何形狀 8
1-4-2 靜電作用效應 9
1-4-3 溶劑環境所影響 9
1-4-4 疏水性程度 10
1-5 陰離子感測器之設計 11
1-6 感測器與陰離子之作用 12
1-6-1 靜電作用力 (Electrostatic interaction) 12
1-6-2 氫鍵作用力 (Hydrogen bond) 14
1-6-3 準分子形成 (Excimer formation) 15
1-6-4 鹵素鍵作用力 (Halogen bond) 17
1-6-5 陰離子-π 作用 (Anion-π interaction) 19
1-7 金屬錯合物 (Metal complex) 28
1-7-1 利用金屬去預測整體分子的結構形狀 28
1-7-2 以金屬為感測中心，陰離子與金屬藉由軌域重疊形成鍵結 29
1-8 過渡金屬錯合物 30
1-9 化學感測器之訊號傳輸 35
1-9-1 以電化學做偵測 (Electrochemical recognition of anions) 35
1-9-2 以光學訊號做偵測 (Optical recognition of anions) 36
1-10 螢光化學感測器 37
1-10-1 光誘導電子轉移 (Photoinduced electron transfer, PET) 37
1-10-2 分子內部電荷轉移 (Intramolecular charge transfer, ICT) 39
1-11 研究動機 42
二、結果與討論 45
2-1 錯合物之結構設計 45
2-2 合成流程圖 47
2-2-1 配體 (Ligand) 47
2-2-2 錸金屬錯合物 (Complex) 49
2-3 化合物BppEb 54
2-3-1 合成方法 54
2-3-2 13C NMR討論 56
2-3-3 單晶結構分析 59
2-4 錯合物Bppb-Re-Ph 61
2-4-1 結構討論與純化方法 61
2-4-2 U型的單晶結構分析 (Bppb-Re-Ph U) 64
2-4-3 U型的基本光物理性質 67
2-4-4 U 型的變溫1H NMR圖譜 69
2-5 錯合物Bppb-Re-L1 71
2-5-1 合成方法 71
2-5-2 純化方法 71
2-6 錯合物BppEb-Re-Ph 73
2-6-1 純化方法與結構討論 73
2-7 錯合物BppEb-Re-L1 74
2-7-1 純化方法與結構討論 74
2-8 錯合物BppEb-Re系列的結構比較 75
2-9 錯合物對陰離子感測行為實驗 76
2-9-1 錯合物Bppb-Re-L1 76
2-9-2 錯合物BppEb-Re-L1 79
三、總結 83
四、實驗部分 85
4-1 實驗儀器與方法 85
4-2 合成步驟 90
4-2-1 化合物 90
4-2-2 錸金屬錯合物 97
五、參考資料 109
附圖119

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指導教授

孫世勝、陳銘洲(Shih-Sheng Sun Ming-Chou Chen)

審核日期

2017-8-18

推文