臺灣博碩士論文加值系統

本論文主要分為三個部分。第一部分的研究利用具有肽鍵(peptides)的雙吡啶橋接配位基，與Au(I)離子進行配位合成[L6(AuPPh3)2](ClO4)2 1、[dppm2(Au)4L62](ClO4)2 2、[dppp2(Au)4L62](ClO4)2 3和[dpppn3(Au)7L63](PF6)7 4 (L6 = N,N’ -Bis-4-methylpyridyl Oxalamide)等Au(I)超分子，並探討其結構及光物理性質。由單晶結構的研究中可知2在結構中具有金…金作用力，其它的Au(I)超分子則不具有金…金作用力。進一步研究其光物理性質，經由與文獻及自由配位基的比較，可知其位於波長 230 ~ 270 nm的吸收及位於波長 420 ~ 515 nm的放光，來源大致是來自配位基PPh3的π→π*或帶有一點Au→PPh3躍遷。第二部分為三核錸化合物(Re(CO)5)3(SSS)(OTf) 5、(Re(CO)5)3(TMT) 6和(Re(CO)5)3(TBBT)(OTf) 7 (OTf = OSO2CF3, SSS = 1,3,4-thiadiazoledithiolate, TMT = 2,4,6-trimercaptotriazinetrithiolate, TBBT = 4,4’-thiobis(benzenethiol))的結構及光譜研究分析。由5的單晶結構中發現其形成三核錸金屬化合物，金屬與金屬之間並沒有作用力存在。另外在其吸收光譜的研究中，推測其位於波長275及335 nm的吸收來源應該是來自配位基本身；而波長380 nm處的吸收則是來自S→Re躍遷。第三部分則是使用硫作為橋接配位基連結三個鈀金屬形成有趣的三角形結構 [Pd3(d-t-bpy)3(μ3-S2)](NO3)2 11和[Pd3(bpy)3(μ3-S2)](ClO4)2 12 (d-t-bpy = 4,4’-di-tert-butyl-2,2’-bipyridine, bpy = 2,2’-bipyridine)。由二者的晶體堆疊比較可以發現，11的diimine由於具有較大的取代基，阻擋了其分子間π…π作用力的形成；而 12上的diimine沒有取代基，其晶體堆疊中存在著分子間的π…π作用力。這部分的研究證明了經由適當的設計配位基，我們可以預期其晶體堆疊的表現，甚至是晶體工程的調控。除了晶體堆疊的探討外，我們也研究了11和12的吸收光譜以了解其光學性質。大致上，其吸收來源是diimine配位基的π→π*，同時能量較低的吸收則是來自S→Pd躍遷。

The research focus in this thesis is classified into three parts. The first part is to use N,N’-Bis-4-mrthylpyridyl Oxalamide (L6) as bridging ligand together with diphosphines toward the construction of gold(I) supermolecules. The crystal structures show that [dppm2(Au)4L62](ClO4)4 (2) and [dppp2(Au)4L62](ClO4)4 (3) form the rectangular macrocycle, while [dpppn3Au7L63]2(PF6)7 (4) forms a one-dimensional coordination polymer. When compared with the spectroscopic and photophysical properties of L6 and gold(I) phosphine chlorides, we reason that the absorptions at 230 ~ 270 nm and emissions at 420 ~ 515 nm might be originated from the π → π* of diphosphines mixing Au → diphosphine charge transfer.
In the second part, we utilize N-heterocyclic thioamide-containing ligands and Re(I) to synthesize a series of Re(I)-thiolates 5-7. These groups of ligands are intriguing in coordination chemistry, since they have various coordination modes in exocyclic sulfur or endocyclic nitrogen atoms. SSS[Re(CO)5]3OTf (5) shows high-energy absorptions at 275 and 335 nm as well as a low-energy absorption band at 380 nm, where the former is attributed to an intraligand transition and the latter a S → Re transition. The diimine ligands (i.e., 4,4’-di-tert-butyl-
2,2’-bipyridine) are also introduced into these coordination compounds to enrich the spectroscopic and photophysical properties.
The third part reports triangulo Pd(II) complexes 11-12 including substituted or simply 2,2’-bipyridine and trply-bridging sulfide ligands. In solid-state packing, the latter has intermolecular π…π interaction whereas the former has not. This work highlights the crystal engineering study may be achieved in this class of interesting triangulo Pd(II) complexes.

總目錄
圖目錄…………………...…………………………...……....III
表目錄………………..………………………………..........VI
附表目錄………………………………………………...…VII
附圖目錄………………………………………………....…VIII
Part І：含雙吡啶金超分子 1
第一章 緒論 1
§1-1 親金性(aurophilicity) 1
§1-2金…金作用力對金超分子結構的影響 3
第二章 含雙吡啶金超分子的合成 9
§2-1 實驗裝置與鑑定方法 9
§2-2 實驗部分 11
合成N, N’-Bis-4-methylpyridyl Oxalamide (L6) 11
合成[dppp2(Au)4L62](ClO4)4 (3) 13
§2-3 結果與討論 14
§2-3-1 單晶結構 14
§2-3-2 吸收光譜與放光光譜 21
§2-4 結論 23
Part ІI：含錸金屬配位化合物 25
第一章 緒論 25
§1-1 硫醇(thiol)配位基 25
§1-2錸金屬-硫醇(thiolate)配位化合物 30
第二章 含錸金屬配位化合物的合成 33
§2-1 實驗部分 34
合成Re(CO)5OTf 34
合成SSS[Re(CO)5]3OTf (5) 35
合成TMT[Re(CO)5]3OTf (6) 35
合成TBBT[Re(CO)5]3OTf (7) 36
合成(d-t-bpy)Re(CO)3Cl 37
合成(d-t-bpy)Re(CO)3OTf 38
合成SSS[(d-t-bpy)Re(CO)3]3OTf (8) 39
合成TMT[(d-t-bpy)Re(CO)3]3 (9) 39
合成TBBT[(d-t-bpy)Re(CO)3]3OTf (10) 40
§2-2 結果與討論 41
§2-2-1 單晶結構 41
§2-2-2 吸收光譜 43
§2-3 結論 45
Part III：鈀金屬配位化合物 47
第一章 緒論 47
§1-1超分子的自組裝 47
§1-2 M3S2核心配位超分子化合物 49
第二章 鈀金屬配位化合物的合成 53
§2-1 實驗部分 54
合成Pd(tBu2bpy)Cl2 54
合成Pd(bpy)Cl2 54
合成(Pd3(tBu2bpy)3)(μ-S2)(NO3)2 (11) 55
合成(Pd3(bpy)3)(μ-S2))(ClO4)2 (12) 56
§2-2 結果與討論 58
§2-2-1 晶體結構 58
§2-2-2 吸收光譜 63
§2-3 結論 64
參考文獻 66

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