本篇主要是探討[Ag7(H){E2P(OiPr)2}6] (E=S，1b；Se，2b) 和[Cu7(H){E2P(OiPr)2}6] (E=S，1a；Se，2a) 兩個氫化物為中心的單金屬簇混合，產生兩個系列以氫化物為中心的雙金屬簇[CuxAg7-x(H){E2P(OiPr)2}6] (x = 1-6；E=S，3a；Se，3b)。透過正電荷ESI-MS光譜並利用多核種的NMR光譜(1H、2H、31P{H}、77Se、109Ag)與X-ray 單晶繞射分析出[CuAg6(H){Se2P(OiPr)2}6](5a)、Cu4Ag3(H){S2P(OiPr)2}6 (4a) 、 [Cu6Ag(H){S2P(OiPr)2}6] (6a) 晶體結構得到充分的表徵。

溶液中單個化合物的的訊號是動態化學平衡的結果，主要是由金屬交換所驅動，實際上團簇間交換反應的過程，在加入1a 和 1b 時產生氫化物為中心的雙金屬簇 (3a) 可以利用濃度依賴性 31P NMR光譜看到，反應中含有濃度較高的 1b 可以看到其分布較為接近 1b 的共振，結果是遵循 Le Chatelier’s 原理，動態平衡由2D交換光譜加以確認，且觀察到金屬逐步的交換過程，證實了化合物在溶液中是以動態平衡的存在。


在合成起使團簇的過程中發現[Ag7(H){S2P(OiPr)2}6]在溶液中會緩慢的轉化成另一種團簇，並且利用加熱誘導[Ag7(H){S2P(OiPr)2}6]自身氧化還原合成出一種新型的兩電子超原子奈米團簇，透過正電荷ESI-MS光譜並利用多種分析技術( NMR光譜(1H、31P、13C)、Uv-vis、螢光光譜儀 ) 與X-ray 單晶繞射分析出[Ag10{S2P(OiPr)2}8]晶體結構得到了充分的表徵，Ag7(H)的金屬骨架屬於雙三角錐並向左右各延伸一個鋒與Ag10有高度相關的，這表示Ag7(H)在合成中扮演了還原劑以及模板的功用。

[Ag7(H){S2P(OiPr)2}6] and [Cu7(H){S2P(OiPr)2}6] hydride-centered monometallic clusters are mixed to produce hydride-centered bimetallic clusters [CuxAg7-x(H){S2P(OiPr)2}6]1 (x = 1-7). Their compositions are fully characterized by positive mode ESI-MS spectrometry, multi-NMR spectroscopy (1H, 2H, 31P{H}, 109Ag , 31P-31P{1H} 2D EXSY) and single crystal X-ray diffraction. This is the first report that intercluster exchanges is applied to the synthesis of hydride-centered bimetallic clusters.

A controllable synthesis under reducing conditions in the preparation of superatoms with cluster electron not exceeding two is challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag 10 {S2P(OiPr)2}8(1), is isolated via a self-redox reaction of Ag7(H){S2 P(OiPr)2}6 without adding extra reducing agents. The metal framework of Ag7, a bicapped trigonal bipyramid, is highly correlated to that of Ag10, suggesting Ag7(H){S2P(OiPr)2}6 as the both reducing agent and a template for cluster growth.

一、 緒論 1
1.1 金屬氫化物 (metal hydride) 1
1.2 簇間反應(Intercluster reaction) 2
1.3 超原子金屬簇(Superatom) 3
二、 實驗部分 6
2.1 溶劑系統 6
2.2 儀器 6
2.3實驗步驟 8
2.3.1 [NH4][S2P(OiPr)2] 配位基合成 8
2.3.2 [NH4][Se2P(OiPr)2] 配位基合成 9
2.3.3 [Cu7(H){S2P(OiPr)2}6] (1a) 的合成 10
2.3.4 [Ag7(H){S2P(OiPr)2}6] (1b) 的合成 10
2.3.5 [Cu7(H){Se2P(OiPr)2}6] ( 2a) 的合成 11
2.3.6 [Ag7(H){Se2P(OiPr)2}6] (2b) 的合成 12
2.3.7[CuxAg7-x(H){S2P(OiPr)2}6] (3a) 的合成 13
2.3.8 [CuxAg7-x(H){Se2P(OiPr)2}6] (3b) 的合成 16
2.3.9 [CuxAg7-x(D){S2P(OiPr)2}6] (3aD)的合成 18
2.3.10 [CuxAg7-x(D){Se2P(OiPr)2}6] (3bD) 的合成 19
2.3.11 [Ag10{S2P(OiPr)2}8的合成 20
三、結果與討論 22
3.1.1 [CuxAg7-x (H){E2P(OiPr)2}6] ( E= S；Se )核磁共振光譜討論 22
3.1.2 [CuxAg7-x (H){E2P(OiPr)2}6] ( E= S；Se )質量圖譜討論 41
3.1.3 [CuxAg7-x (H){E2P(OiPr)2}6] ( E=S；Se )晶體結構討論 45
3.2.1 Ag10{S2P(OiPr)2}8核磁共振光譜探討 49
3.2.2 Ag10{S2P(OiPr)2}8質量光譜探討 58
3.2.3 Ag10{S2P(OiPr)2}8光物理性質探討 59
3.2.4 Ag10{S2P(OiPr)2}8 XPS光譜討論 64
3.2.5 Ag10{S2P(OiPr)2}8晶體結構探討 66
五、 參考文獻 71
附錄 76

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