第一章節：自組裝過程中的模板體積效應:有機硫(硒)化磷配位基保護之含鹵素銀簇：合成一系列在正方體金屬骨架中心含有鹵素原子之八核銀團簇，[Ag8(X){E2P(C2H4Ph)2}6]PF6, X = F (1), Cl (2), Br (3), E = S; X = F (5), Cl (6), Br (7), E = Se，藉由改變鹵素原子的大小，使得鹵素原子周圍的正方體金屬骨架會隨著中心模板體積變大而造成金屬架擴張，直至加入更大的碘離子，無法維持八核銀所構成的正方體骨架無法容納碘離子，進而形成十二核銀團簇，[Ag12(I)5{E2P(C2H4Ph)2}6](I), E = S (4), Se (8)，並且伴隨著放光現象。
第二章節：多氫銅團簇之X光及中子繞射研究：五個多氫銅團簇化合物：[Cu20(H)11{S2P(OiPr)2}9] (9)、[Cu32(H)20{S2P(OiPr)2}12] (10)、[Cu20(H)11{Se2P(OiPr)2}9] (11)、[Cu36(H)21{S2P(OiPr)2}12]PF6 (12)、 [Cu36(D)19Cl2{S2P(OiBu)2}12]PF6 (13)，藉由單晶X光繞射及中子繞射實驗鑑定氫負離子的數量及其準確位置。

Chapter 1: A Size Effect in Self-Assembly Process: Halide-Encapsulated Silver(I) Clusters Stabilized by Dichalcogenophosphinate Ligands: We synthesized a serious of the following new compounds, [Ag8(μ8-X){E2P(CH2CH2Ph)2}6](PF6) (E = S, X = F (1), Cl (2), Br (3); E = Se, X = F (5), Cl (6), Br (7)), and the first example of cuboctahedron Ag12. skeleton, [Ag12(μ12-I)(μ3-I)4{E2P(CH2CH2Ph)2}6](I) E = S (4), Se (8), with a μ12-iodide in the center by experimental and theoretical investigations.
Chapter 2: X-ray and Neutron Diffraction Studies of Copper Hydride Clusters: Locate the number and the location of hydride atoms by single-crystal X-ray and neutron diffraction in five copper hydride clusters, [Cu20(H)11{S2P(OiPr)2}9] (9), [Cu32(H)20{S2P(OiPr)2}12] (10), [Cu20(H)11{Se2P(OiPr)2}9] (11), [Cu36(H)21{S2P(OiPr)2}12]PF6 (12), and [Cu36(D)19Cl2{S2P(OiBu)2}12]PF6 (13).

Chapter 1. A Size Effect in Self-Assembly Process: Halide-Encapsulated Silver(I) Clusters Stabilized by dichalcogenophosphinate Ligands……………………………1

1.1 Introduction…………………………………………………………………..1
1.2 Results and Discussions…………………………………………………...…3
1.2.1 X -ray Diffraction Studies……………………………….……………..4
1.2.2 NMR Studies…………………………………………………………...8
1.2.3 ESI-Mass Spectroscopy Studies……………………………………….9
1.2.4 Computational Results of compound 4……………………………….11
1.2.5 Photophysical Studies…………………………………………….…..14
1.3 Conclusions………………………………………………………………....18
1.4 Experimental Section…………………………………………………….....19
1.4.1 Synthesis……………………………………………………………..19
1.4.2 X-ray Crystallography……………………………………………….22
1.4.3 Computational Details……………………………………………….25

Chapter 2. X-ray and Neutron Diffraction Studies of Copper Hydride Clusters…….27

2.1 X-ray and Neutron Diffraction……………………………………………...27
2.2 Copper Hydride……………………………………………………………..34
2.3 Neutron Diffraction Study of [Cu20(H)11{S2P(OiPr)2}9]……………………38
2.3.1 Experimental Section………………………………………………..38
2.3.2 Results and Discussions……………………………………………..43
2.4 Neutron Diffraction Study of [Cu32(H)20{S2P(OiPr)2}12]……...……………52
2.4.1 Experimental Section………………………………………………..52
2.4.2 Results and Discussions……………………………………………..58
2.5 Neutron Diffraction Study of [Cu20(H)11{Se2P(OiPr)2}12]……......…….…..64
2.5.1 Experimental Section……………………………………………….64
2.5.2 Results and Discussions…………………………………………….71
2.6 Neutron Diffraction Study of [Cu36(H)21{S2P(OiPr)2}12](PF6)…...…….….77
2.6.1 Experimental Section………………………………………………...77
2.6.2 Results and Discussions……………………………………………...81
2.7 Neutron Diffraction Study of [Cu36(D)19Cl2{S2P(OiBu)2}12](PF6)..…….….86
2.7.1 Experimental Section………………………………………………..86
2.7.2 Results and Discussions………………………………………….….90
2.8 Conclusions………………………………………………………………...95

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