以實驗室於最近發表的8電子超原子結構[Pt(H)Ag19{S2P(OR)2}12] (R = nPr, iPr) 1作為基礎。本篇使用同樣為過渡金屬第10族元素Pd，結合新的合成策略，通過共還原法(Co-reduction method)、一鍋合成法(one-plot synthesis)和配體置換法，合成含有氫化物之鈀-銀雙金屬合金奈米團簇[Pd(H)Ag19{E2P(OR)2}12] (E = S, Se；R = iPr, iBu)，在合成的過程中，會得到副產物[PdAg20{S2P(OR)2}12] (R = iPr, iBu)，其中[PdAg20{S2P(OiBu)2}12]的晶體結構不同於過去實驗室發表的[PdAg20{S2P(OnPr)2}12] 2，[PdAg20{S2P(OiBu)2}12]屬於C3對稱性的結構。在後續的實驗中表明[Pd(H)Ag19]和[PdAg20]之間是有關聯的，[Pd(H)Ag19{E2P(OR)2}12]在高溫下會轉變成[PdAg20{E2P(OR)2}12]，並且發現[Pd(H)Ag19{S2P(OiPr)2}12]在酸性條件下，會部分解離並重組成新的含氫化物奈米團簇[Pd(H)Ag20{S2P(OiPr)2}12]，最後合成氘代類似物以及利用ESI-MS和NMR以證實氫化物的存在，使用UV-Vis和X-ray等儀器來鑑定這些奈米團簇。本實驗所得的含氫化物奈米團簇皆屬於8電子的超原子結構，其中hydride都以H+的方式存在於團簇中。

摘要 i
目錄 iii
反應式 vi
表目錄 vi
一、緒論 1
1.1 奈米團簇 (Nanocluster) 1
1.2 超原子模型 (Superatom model) 2
1.3 金屬氫化物奈米團簇 3
二、實驗部分 7
儀器 7
實驗合成 9
2.1 [Pd(H)Ag19{S2P(OiPr)2}12]的合成 9
2.2 [Pd(H)Ag19{S2P(OiBu)2}12]的合成 10
2.3 [Pd(H)Ag19{Se2P(OiPr)2}12]的配體置換合成 11
2.4 [Pd(H)Ag20{S2P(OiPr)2}12](PF6)的合成 12
2.5 [Pd(D)Ag19{S2P(OiPr)2}12]的合成 13
2.6 [Pd(D)Ag19{Se2P(OiPr)2}12]的合成 13
2.7 [Pd(D)Ag20{S2P(OiPr)2}12](PF6)的合成 13
三、結果與討論 15
3.1. [Pd(H)Ag19{S2P(OR)2}12] (R = iPr, iBu)的合成 15
3.2. [Pd(H)Ag19{S2P(OiPr)2}12]的結構 16
3.2.1 [Pd(H)Ag19{S2P(OR)2}12] (R = iPr, iBu)光譜與質譜分析 19
3.3. [PdAg20{S2P(OiBu)2}12]的結構 29
3.3.1 [PdAg20{S2P(OiBu)2}12]的光譜與質譜分析 32
3.4 [Pd(H)Ag19{Se2P(OiPr)2}12]的配體置換合成與結構 37
3.4.1 [Pd(H)Ag19{Se2P(OiPr)2}12]的光譜與質譜分析 40
3.5 [Pd(H)Ag20{S2P(OiPr)2}12](PF6)的合成與結構 46
3.5.1 [Pd(H)Ag20{S2P(OiPr)2}12](PF6)的光譜與質譜分析 50
3.6 綜合比較 61
3.6.1 結構 61
3.6.2 NMR光譜 63
3.6.3 吸收光譜與螢光光譜 64
3.6.4 XPS 72
四、結論 79
五、參考文獻 81
圖錄
Figure 1 使用TLC (DCM:ether = 3:1)分離[Pd(H)Ag19]和[PdAg20] 15
Figure 2 [Pd(H)Ag19{S2P(OiPr)2}12]: (a)二十面體PdH@Ag12金屬核(b) hydride佔據四面體的空隙 16
Figure 3 [Pd(H)Ag19{S2P(OiPr)2}12]的PdH@Ag12@Ag7金屬骨架 17
Figure 4 [Pd(H)Ag19{S2P(OiPr)2}12]去除異丙氧基的整個分子結構 18
Figure 5 [Pd(H)Ag19{S2P(OiPr)2}12]的31P NMR (161.97 MHz, CDCl3) 室溫光譜圖 19
Figure 6 [Pd(H)Ag19{S2P(OiBu)2}12]的31P NMR (161.97 MHz, CDCl3) 室溫光譜圖 20
Figure 7 [Pd(H)Ag19{S2P(OiPr)2}12]的31P NMR (242.83 MHz, CD2Cl2) 變溫光譜圖 21
Figure 8 [Pd(H)Ag19{S2P(OiPr)2}12]的1H NMR (600 MHz, CD2Cl2) 室溫光譜圖 23
Figure 9 [Pd(D)Ag19{S2P(OiPr)2}12]的2H NMR (61.42 MHz, CHCl3) 光譜圖 23
Figure 10 [Pd(H)Ag19{S2P(OiBu)2}12]的1H NMR (400 MHz, CDCl3) 24
Figure 11 [Pd(H)Ag19{S2P(OiPr)2}12]的1H NMR (600 MHz, CD2Cl2) 25
Figure 12 [Pd(H)Ag19{S2P(OiPr)2}12]的正電荷ESI-TOF-MS (ES+) 質譜圖 26
Figure 13 [Pd(D)Ag19{S2P(OiPr)2}12]的正電荷ESI-TOF-MS (ES+) 質譜圖 27
Figure 14 [Pd(H)Ag19{S2P(OiBu)2}12]的正電荷ESI-MS質譜圖 28Figure 15 [PdAg20{S2P(OiBu)2}12]的二十面體PdH@Ag12金屬核 29
Figure 16 [PdAg20{S2P(OiBu)2}12]的Pd@Ag12@Ag8金屬骨架 30
Figure 17 [PdAg20{S2P(OiBu)2}12]去除異丁氧基的整個分子結構 31
Figure 18 [PdAg20{S2P(OiBu)2}12]的31P NMR (161.97 MHz, CDCl3) 光譜圖 32
Figure 19 [PdAg20{S2P(OiBu)2}12]的1H NMR (300 MHz, CDCl3) 光譜圖 33
Figure 20 [PdAg20{S2P(OiBu)2}12]的正電荷ESI-MS質譜圖 34
Figure 21[Pd(H)Ag19{S2P(OiPr)2}12]在333 K下 (CDCl3) 隨著時間hydride逐漸消失 35
Figure 22 [Pd(H)Ag19{S2P(OiPr)2}12] (101.37 ppm)在333 K (CDCl3) 隨著時間轉變成[PdAg20{S2P(OiPr)2}12] (100.43 ppm) 36
Figure 23[Pd(H)Ag19{Se2P(OiPr)2}12]: (a)二十面體PdH@Ag12金屬核(b) hydride佔據四面體的空隙 37
Figure 24 [Pd(H)Ag19{Se2P(OiPr)2}12]的PdH@Ag12@Ag7金屬骨架 38
Figure 25 [Pd(H)Ag19{Se2P(OiPr)2}12]的去除異丙氧基的分子結構 39
Figure 26 [Pd(H)Ag19{Se2P(OiPr)2}12]的31P NMR (161.97 MHz, CDCl3) 室溫光譜圖 40
Figure 27 [Pd(H)Ag19{Se2P(OiPr)2}12]的4組配位基化學環境 41
Figure 28. [Pd(H)Ag19{Se2P(OiPr)2}12]的31P NMR (242.83 MHz, CD2Cl2) 變溫光譜圖 42
Figure 29 [Pd(H)Ag19{Se2P(OiPr)2}12]的1H NMR (600 MHz, CD2Cl2) 43
Figure 30 [Pd(D)Ag19{Se2P(OiPr)2}12]的2H NMR (61.42 MHz, CHCl3) 光譜圖 43
Figure 31 [Pd(H)Ag19{Se2P(OiPr)2}12]的1H NMR (600 MHz, CD2Cl2) 44
Figure 32 [Pd(H)Ag19{Se2P(OiPr)2}12]的正電荷ESI-MS質譜圖 45
Figure 33 [Pd(H)Ag20{S2P(OiPr)2}12]+的二十面體PdH@Ag12金屬核 46
Figure 34 [Pd(H)Ag20{S2P(OiPr)2}12]+的PdH@Ag12@Ag8金屬核 47
Figure 35 [Pd(H)Ag20{S2P(OiPr)2}12]+的去除異丙氧基的分子結構 48
Figure 36 [Pd(H)Ag20{S2P(OiPr)2}12](PF6)的31P NMR (161.97 MHz, (CD3)2CO) 室溫光譜圖 50
Figure 37 [Pd(H)Ag20{S2P(OiPr)2}12]+的31P NMR (242.83 MHz, (CD3)2CO) 變溫光譜圖 52
Figure 38 [Pd(H)Ag20{S2P(OiPr)2}12]+的31P NMR (242.83 MHz, CD2Cl2) 變溫光譜圖 53
Figure 39 [Pd(H)Ag20{S2P(OiPr)2}12]+的1H NMR (400 MHz, (CD3)2CO)室溫光譜圖 54
Figure 40 [Pd(H)Ag20{S2P(OiPr)2}12]+的2H NMR (61.42 MHz, CH2Cl2) 光譜圖 55
Figure 41 [Pd(H)Ag20{S2P(OiPr)2}12]+的1H NMR(600 MHz, (CD3)2CO) 56
Figure 42 [Pd(H)Ag20{S2P(OiPr)2}12]+的1H NMR (600 MHz, CD2Cl2) 57
Figure 43[Pd(H)Ag20{S2P(OiPr)2}12]+的正電荷ESI-TOF-MS (ES+) 質譜圖 58
Figure 44 [Pd(H)Ag20{S2P(OiPr)2}12]+的31P NMR (161.97 MHz, CDCl3) 在333 K定溫變時光譜圖 60
Figure 45 含氫化物的二十面體核: (a)[Pd(H)Ag19{S2P(OiPr)2}12], (b) [Pd(H)Ag19{Se2P(OiPr)2}12], (c)[Pd(H)Ag20{S2P(OiPr)2}12]+ 61
Figure 46 二十一個金屬組成的金屬核: (a)[Pd(H)Ag20{S2P(OiPr)2}12]+, (b) [Ag21{S2P(OiPr)2}12]+, (c)[PdAg20{S2P(OiBu)2}12], (d)[PdAg20{S2P(OnPr)2}12] 62
Figure 47 二十面體金屬核Agico-Agico鍵長比較 63
Figure 48 [Pd(H)Ag19{S2P(OiPr)2}12]和[PdAg20{S2P(OiBu)2}12]的吸收光譜比較圖 64
Figure 49 [PdAg20{S2P(OiBu)2}12]的吸收和放光光譜 65
Figure 50 [PdAg20{S2P(OiBu)2}12]的時間分辨光致發光光譜圖 66
Figure 51 [Pd(H)Ag19{Se2P(OiPr)2}12]的吸收和放光光譜 67
Figure 52 [Pd(H)Ag19{Se2P(OiPr)2}12]的時間分辨光致發光光譜圖 68
Figure 53 [Pd(H)Ag19{E2P(OiPr)2}12] (E = S, Se)的吸收光譜比較圖 69
Figure 54 [Pd(H)Ag19{S2P(OiPr)2}12]和[Pd(H)Ag20{S2P(OiPr)2}12]+的吸收光譜比較圖 70
Figure 55 同樣為20個金屬組成的奈米糰簇的吸收光譜比較圖 71
Figure 56 Ag 3d的XPS光譜圖: (a) [Pd(H)Ag19{S2P(OiPr)2}12], (b) [Pd(H)Ag19{Se2P(OiPr)2}12] 72
Figure 57 Pd 3d的XPS光譜圖: (a) [Pd(H)Ag19{S2P(OiPr)2}12], (b) [Pd(H)Ag19{Se2P(OiPr)2}12] 73
反應式
Scheme 1 [Pd(H)Ag19{S2P(OR)2}12] (R = iPr, iBu)的合成反應路徑 15
Scheme 2 [Pd(H)Ag19{Se2P(OiPr)2}12]的合成路徑 37
Scheme 3 [Pd(H)Ag20{S2P(OiPr)2}12](PF6)的合成路徑 46
表目錄
Table 1 鈀銀奈米合金團簇的NMR光譜比較 63
Table 2 Pd-Ag NCs 吸收與放光訊號比較圖 71
Table 3 [Pd(H)Ag19{E2P(OiPr)2}12] (E = S, Se)的Ag 3d殼層XPS比較 73
Table 4 [Pd(H)Ag19{E2P(OiPr)2}12] (E = S, Se)的Pd 3d殼層XPS比較 73
Table 5 Crystal data and structure refinement for [Pd(H)Ag19{S2P(OiPr)2}12] (NDHU210080) 74
Table 6 Crystal data and structure refinement for [PdAg20{S2P(OiBu)2}12] (NDHU200103) 75
Table 7 Crystal data and structure refinement for [Pd(H)Ag19{Se2P(OiPr)2}12] (NDHU210004) 76
Table 8 Crystal data and structure refinement for [Pd(H)Ag20{S2P(OiPr)2}12]+ (NDHU220022) 77
Table 9 Bond lengths (Å) and angles (deg.) for [Pd(H)Ag19{S2P(OiPr)2}12] 88
Table 10 Bond lengths (Å) and angles (deg.) for [PdAg20{S2P(OiBu)2}12] 116
Table 11 Bond lengths (Å) and angles (deg.) for [Pd(H)Ag19{Se2P(OiPr)2}12] 126
Table 12 Bond lengths (Å) and angles (deg.) for [Pd(H)Ag20{S2P(OiPr)2}12]+ 151

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