Series of bimetallic alloy copper-rich cluster are produced from a reaction of polyhydrido copper such as [Cu28H15{S2CNnBu2}12](PF6), [Cu20H11{S2P(OiPr)2}9], and [Cu20H11{S2P(CH2CH2Ph)2}9] and various amounts of phenylacetylene with metal salts such as Au(PPh3)Cl, [Ag(CH3CN)4](PF6), Pd(CH3CN)2Cl2, and [Pt{S2P(OnPr)2}2]. The discussion is divided into four parts, namely: 1) synthesis and characterization of two electron bimetallic alloy copper clusters from the reaction of copper polyhydrides with eleven- and fifteen-equivalence of phenylacetylene along with metal (Au and Ag) salt, which generate several new clusters, like: [Cu13{S2CNnBu2}6(C≡CPh)4]+ (1), [AuCu12{S2CNR2}6(C≡CPh)4]+ (R = nBu (2) and nPr (3)), [AuCu12{S2P(OiPr)2}6(C≡CPh)4]+ (4), [AuCu12{S2P(CH2CH2Ph)2}6(C≡CPh)4]+ (5), [AgCu12{S2CNnBu2}6(C≡CPh)4]+ (6), and [AgCu12{S2P(OiPr)2}6(C≡CPh)4]+ (7). All these clusters have a M@Cu12 (M = Cu, Au, and Ag) cuboctahedral core. The doping of Au atoms into copper polyhydrides can enhance photoluminescence properties by increasing the percentage yield luminescent 32% at room temperature. 2) by using similar synthetic strategies, the amount of phenylacetylene can be reduced into nine- and ten-equivalence along with metal (Pd and Pt) salts into the copper polyhydrides and can also generate new copper-rich bimetallic cluster encapsulated by linear metal dihydride MH2@Cu14 (M = Cu, Pd and Pt), such as [CuH2@Cu14{S2CNnBu2}6(C≡CPh)6]+ (8), [MH2@Cu14{S2CNnBu2}6(C≡CPh)6] (M = Pd (9)32 and Pt (10)), and [MH2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (M = Pd (11)32 and Pt (12)). 3) using nine-equivalence of phenylacetylene can also produce copper hydrides cluster which containing hydrides in trigonal pyramidal geometry [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (13).53 This is the first copper cluster encapsulated hydrides in pentacapped trigonal prism and as template in the fabrication of copper-rich alloys cluster. We conduct reaction of formic acid with our copper hydrides to produce H2 and CO2 gases as the dehydrogenation reaction. Furthermore, this research can be expanded to use [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (13) as a template to generate bimetallic copper-rich alloy cluster by inserting a metal ion such as Cu, Au, Ag, and Pd into the Cu11 cage, to generate brand new [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (14), [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (15), [AgH2Cu14{S2P(OiPr)2}6(C≡CPh)6]+ (16), [PdHCu11{S2P(OiPr)2}6(C≡CPh)4] (17). In this work, we realize that the hydrides inside Cu11 cage have dual roles as ligands (14, 16 and 17) and as reducing agents (15). Insertion of Cu atom into compound 13 will lead formation of copper dihydride inside Cu11H¬ cage. This is the first copper cluster containing linear copper dihydrides in pentacapped trigonal prism. Subsequently, insertion of Au atom into Cu11H2 cage will enhance the emission quantum yield by up to 3.3% in room temperature. Meanwhile insertion of Pd will lead to form Pd-Cu bimetallic cluster (17), which is effective a catalyst for C-C bond coupling reaction such as Sonogashira reaction with an excellent yield (96%).

Abstract I
List of Content III
List of Figure IX
List of Scheme XIII
List of Appendix XV
List of Table XXV
Chapter I. Introduction 1
Chapter II: Experimental Section 17
2.1. Instrument 17
2.2. Procedure 20
2.2.1. Synthesis of [Cu@Cu12{S2CN(nBu)2}6(C≡CPh)4](CuCl2) (1) 20
2.2.2. Synthesis of [Au@Cu12{S2CNnBu2}6(C≡CPh)4](CuCl2) (2) 20
2.2.3. Synthesis of [Au@Cu12{S2CNnPr2}6(C≡CPh)4](CuCl2) (3) 21
2.2.4. Synthesis of [Ag@Cu12{S2CNnBu2}6(C≡CPh)4](PF6) (4) 22
2.2.5. Synthesis of [Au@Cu12{S2P(OiPr)2}6(C≡CPh)4](CuCl2) (5) 23
2.2.6. Synthesis of [Au@Cu12{S2P(CH2CH2Ph)2}6(C≡CPh)4](CuCl2) (6) 24
2.2.7. Synthesis of [Ag@Cu12{S2P(OiPr)2}6(C≡CPh)4](PF6) (7) 25
2.2.8. Synthesis of [CuH2@Cu14{S2CNnBu2}6(C≡CPh)6] (8H) 25
2.2.9. Synthesis of [CuD2@Cu14{S2CNnBu2}6(C≡CPh)6] (8D) 26
2.2.10. Synthesis of [PdH2@Cu14{S2CNnBu2}6(C≡CPh)6] (9H) 27
2.2.12. Synthesis of [PtH2@Cu14{S2CNnBu2}6(C≡CPh)6] (10H) 28
2.2.13. Synthesis of [PtD2@Cu14{S2CNnBu2}6(C≡CPh)6] (11D) 29
2.2.14. Synthesis of [PdH2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (11H) 29
2.2.15. Synthesis of [PdD2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (11D) 30
2.2.16. Synthesis of [PtH2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (12H) 31
2.2.17. Synthesis of [PtD2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (12D) 31
2.2.18. Synthesis of [Cu11H2{S2P(OiPr)2}6(C≡CPh)6] (13H) 32
2.2.19. Synthesis of [Cu11D2{S2P(OiPr)2}6(C≡CPh)6] (13D) 33
2.2.20. Synthesis of [Cu@Cu11 H2{S2P(OiPr)2}6(C≡CPh)3](PF6) (14H) 34
2.2.21. Synthesis of [Cu@Cu11D2{S2P(OiPr)2}6(C≡CPh)3](PF6) (14D) 35
2.2.22. Synthesis of [Au@Cu11{S2P(OiPr)2}6(C≡CPh)3Cl] (15) 36
2.2.23. Synthesis [AgH2@Cu14{S2P(OiPr)2}6(C≡CPh)6](PF6) (16H) 37
2.2.24. Synthesis [AgD2@Cu14{S2P(OiPr)2}6(C≡CPh)6](PF6) (16D) 38
2.2.25. Synthesis of [PdH@Cu11{S2P(OiPr)2}6(C≡CPh)4] (17H) 38
2.2.26. Synthesis [PdD@Cu11{S2P(OiPr)2}6(C≡CPh)4] (17D) 39
Chapter III. Results and Discussion 41
3.1. Two-Electron Superatom and Bimetallic Alloy Copper-rich Compounds by using Copper Hydrides as Precursor 41
3.1.1. Preparation of Compounds [M@Cu12{S2CNR2}6(C≡CPh)4](CuCl2) (M = Cu (1), Au (2, 3) and Ag (4); R = nBu (1, 2, 4), nPr (3) 41
3.1.2. Preparation of Compounds [M@Cu12{S2PR2}6(C≡CPh)4](CuCl2) (M = Au (5, 6) and Ag (7); R = OiPr (5, 7), CH2CH2Ph (6) 44
3.1.3. NMR Spectroscopic Studies of Compounds 1-7 45
3.1.4. FT-IR of Compounds 1-7 51
3.1.5. ESI-MS of Compounds 1-7 51
3.1.6. Molecular Structure of Compound 1-5 52
3.1.7. Optical Properties of Compound 1-7 58
3.1.8. X-ray Photoelectron Spectroscopy of Compound 1-6 59
3.1.9. Cyclic Voltammogram and Differential Pulse Voltammograms of Compounds 2, 3, 5, and 6 61
3.1.10. Luminescence Properties of Compounds 1-7 62
3.1.11. Conclusion 66
3.2. 15-Nuclear Copper Dihydride and Bimetallic Alloy Linear Metal Dihydride inside a 14-Copper Cage by Using Copper Polyhydrido as Precursor 67
3.2.1. Preparation of Compounds [Cu(E)2@Cu14{S2CNnBu2}6(C≡CPh)6]+ (8) (E= H (8H) and D (8D)) 67
3.2.2. Preparation of Compounds [ME2@Cu14{S2CNnBu2}6(C≡CPh)6] (M= Pd (9) and Pt (10)) (E= H (9H; 10H) and D (9D; 10D)) 68
3.2.3. Preparation of Compounds [ME2@Cu14{S2P(OiPr)2}6(C≡CPh)6] (M= Pd (11) and Pt (12)) (E= H (11H; 12H) and D (11D; 12D)) 70
3.2.4. NMR Spectroscopic Studies of Compounds 8 - 12 72
3.2.5. ESI-MS of Compounds 8-12 80
3.2.6. FT-IR Spectroscopic Studies of Compounds 9-12 82
3.2.7. Molecular Structures of Compounds 8, 9, 10, and 12 83
3.2.8. Optical Properties of Compounds 8-12 91
3.2.9. Luminescence Properties of Compounds 9 and 11 93
3.2.10. X-ray Photoelectron Spectroscopy (XPS) of Compounds 9 and 10 94
3.2.11. Conclusion 94
3.3. Copper Cluster Containing Hydrides in Trigonal Pyramidal Geometry [Cu11E2{S2P(OiPr)2}6(C≡CPh)3], where E = H (13H) and D (13D) 97
3.3.1. Preparation of Compounds 13H and 13D 97
3.3.2. NMR Studies of Compounds 13H and 13D 99
3.3.3. ESI-MS of Compounds 13H and 13D 101
3.3.4. Molecular Structure of Compound 13 101
3.3.5. FT-IR of Compounds 13H and 13D 106
3.3.6. Photophysical Properties and Stability of Compounds 13H and 13D 106
3.3.7. Conclusion 108
3.4. Linear Copper Dihydrides in Pentacapped Trigonal Prismatic and Bimetallic Alloy Copper-rich Compounds by using [Cu11H2{S2P(OiPr)2}6(C2Ph)3] as A Template 109
3.4.1. Preparation of Compounds [Cu12E2{S2P(OiPr)2}6(C2Ph)3](PF6), where E = H (14H) and D (14D) 109
3.4.3. NMR Studies of Compounds 14H and 14D 110
3.4.4. ESI-MS of Compounds 14H and 14D 112
3.4.5. Molecular Structure of Compound 14 113
3.4.6. Optical Properties of Compounds 14H and 14D 119
3.4.7. Stability and Reactivity of Compound 14 119
3.4.8. Preparation of Compound [Au@Cu11{S2P(OiPr)2}6(C≡CPh)3Cl] (15) 125
3.4.9. NMR Studies of Compound 15 126
3.4.10. ESI-MS of Compound 15 127
3.4.11. Molecular Structure of Compound 15 127
3.4.12. FT-IR of Compound 15 130
3.4.13. Optical Properties of Compound 15 131
3.4.14. Luminescence Properties of Compound 15 131
3.4.15. Reactivity of Compound 15 133
3.4.16. Preparation of Compounds [AgE2@Cu14{S2P(OiPr)2}6(C≡CPh)6]+, where E = H (16H); D (16D). 137
3.4.17. NMR Spectroscopy of Compounds16H and 16D 138
3.4.18. ESI-MS of Compounds 16H and 16D 143
3.4.19. Molecular Structure of Compound 16 143
3.4.20. FT-IR of Compound 16 147
3.4.21. Optical Properties of Compound 16 147
3.4.22. Luminescence Properties of Compound 16 148
3.4.23. Degradation of Compound [AgH2@Cu14{S2P(OiPr)2}6(C≡CPh)6]+ (16H) into [Ag@Cu12{S2P(OiPr)2}6(C≡CPh)4]+ (7) 149
3.4.24. Preparation of [PdE@Cu11{S2P(OiPr)2}6(C≡CPh)4], where E = H (17H); D (17D) 154
3.4.25. NMR Studies of Compounds 17H and 17D 155
3.4.26. ESI-MS of Compounds 17H and 17D 157
3.4.27. FT-IR of Compound 17 157
3.4.28. Molecular Structure of Compound 17 157
3.4.29. Optical Properties of Compound 17 161
3.4.30. Catalytic Performance of Compound 17 in Sonogashira Reaction 162
3.4.31. Conclusion 163
Chapter IV. Conclusion 165
Chapter V. References 167
Appendix 193

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