臺灣博碩士論文加值系統

中文摘要
本論文主要分為兩個部份。第一個部分為有機-無機配位高分子和超分子化合物的合成，在此我們選用了N,N’-Bis-4-methylpyridyl Oxalamide (L6)、N1,N3-di(pyridin-4-yl)isophthalamide (L7)、及N1,N3,N5- tri(pyridin -3-yl)benzene-1,3,5-tricarboxamide (L11’)三種不同的醯胺(pyridyl-amide)配位基和d10 (M=Zn2+、Cd2+、Ag+)的過渡金屬鹽類進行反應。其中利用L6和ZnX2 (X= Br, I)進行反應分別得到了一維的配位高分子[ZnBr2(L6)2]n (1)和超分子矩形[ZnI2(L6)2] (2)，並經由單晶x-ray解析確定其固態結構，有趣的是兩個化合物在空間中的堆疊都具有一維的通道性質。將化合物(2)加熱至攝氏250度三小時，超分子矩形的結構崩解，取而代之的是[ZnI2(L6)]n (3)一維配位高分子結構。使用L6和Cd(II)X2 (X= OAc, NO3,)進行反應分別得到了兩個二維的配位高分子，[Cd(OAc)2 (L6)2(H2O)]n (4)、[Cd(NO3)2(L6)3]n (5)。利用L7和ZnX2 (X=Cl, Br, I)進行反應分別得到了一維的配位高分子[ZnCl2(L7)2]n (6)、[ZnBr2(L7)2]n (7)、[ZnI2(L7)2]n (8)。雖然無法像(1)、(2)一樣，會因為陰離子的不同而造成配位高分子和超分子化合物的差別，但是陰離子的不同還是造成了化合物(6)、(7)、(8)在空間上排列的不同，化合物(6)的空間群為P-1，化合物(7)、(8)的空間群為P21/C。
利用N1,N3,N5- tri(pyridin -3-yl)benzene-1,3,5-tricarboxamide (L11’)和AgPF6反應可得到有趣的二維層狀配位高分子，其空間中的堆疊利用三種分子間的弱作用力，即Ag+…F弱作用力、Ag+×××p弱作用力、DMF溶劑分子和配位基上的amide官能基之間的氫鍵作用力。
第二部分為錸金屬錯化合物的光誘導電子轉移現象探討。我們合成了兩個系列的含錸金屬錯化合物，利用Re(CO)5Cl和2,2’-bis-(4,5-di methyl-imidazole)、2-pyridin-2-yl-1H- benzoimidazole反應後得到的錯化合物在酸性或中性的情況下具有3MLCT的發光性質，但是在鹼性的情況下會因為光誘導電子轉移的現象發生而造成3MLCT的放光會發生淬滅現象，導致放光強度降低。對這些錯化合物而言，配基裡的胺官能基就像是個螢光的開關，此開關的on/off受到酸鹼度的控制。我們也可以將AuPPh3+視為是H+，所以化合物[Re(CO)3(NO3) (py-bimAuPPh3)](12)、[Re(CO)3(NO3) (tm-biimAuPPh3)](15)會和質子化的錯化合物[Re(CO)3Cl(py-bimH)] (10)、[Re(CO)3Cl(tm-biimH2)] (13)一樣具有3MLCT的放光性質。但是Na[Re(CO)3Cl(py-bim)](11)、Na2[Re(CO)3Cl(tm-biim)](14)，則不具有3MLCT的放光性質。其中特別的是化合物(10)可作為陰離子，及化合物(11)可作為陽離子辨識的探討。

Abstract
Supramolecular coordination compounds of Zn2+ and Cd2+ with pyridyl-amide ligand, L6 and L7, have been isolated and their crystal structures determined by X-ray diffraction studies. Anion influence on the structures of metal-organic frameworks has been observed. The reaction of L6 with ZnCl2 and ZnBr2 leads to the formation of 1D coordination polymer, but for ZnI2 a discrete macrocycle is obtained. Although the L7 ligand coordinating to zinc halide can not produce so much difference compared with the L6 ligand system, but different anions also resulted in different space group, P21/C for Cl, P-1 for Br and I, suggesting different structural packing in the solid state.
Except dipyridyldiamides, we also have utilized tripyridyltriamide, L11’ as a tridentate bridging ligand. The reaction of AgPF6 with L11’ leads to a 2-D coordination polymer. The 48-membered macrocycles constructed from three-coordinate AgI ions as connectors and three
tripyridyltriamide moieties propagate into 2-D extended structures.
We have also synthesized a series of Re-based coordination compounds with 2-Pyridin-2-yl-1H-benzoimidazole and 2,2’-bis- (4,5-dimethyl imidazole ). These compounds display luminescence properties in an acidic condition but in a basic condition the properties are quenched. The luminescence quenching mechanism is suggested due to deprotonation of imidazole, where photo induced electron transfer happens to quench the luminescence. The anion and cation recognition studies have also been carried in these.

總目錄
圖目錄…………………………………………………………………..IV
表目錄…………………………………………………………………VII
附圖目錄………………………………………………………….…..VIII
附表目錄………………………………………………..………………X中文摘要…………………………………………..…………………...XI
英文摘要…………………………………………………………..….XIII
實驗裝置及鑑定方法………………………………………………..XIIII
實驗藥品……………………………………..………………………..XV
PART I : Anion-Directed Assembly & Supramolecular Isomerism for Zn2+ and Cd2+ Complexes
第一章 序論…………..………..…………………................................1
§ 1-1超分子的簡介………..…………………………………......................….……..1
§ 1-2晶體工程及有機－無機配位高分子…………………………………...…..…..4
§ 1-2-1晶體工程（Crystal Engineering）……..……………………………..…...….4
§ 1-2-2有機－無機配位高分子（Inorganic－Organic Coordination Polymers）…...5
§ 1-2-3陰離子效應…………..…………………………..………...………………….7
§ 1-3孔洞性材料及其應用………….………………………………………………10
§ 1-4研究動機……………………………………………………………………….17
第二章 合成……………………………….…………………………18
§ 2-1配位基的合成……………………………………………………………….....18
§ 2-1-1合成N,N’-Bis-4-methylpyridyl Oxalamide (L6)…………………………….18
§ 2-1-2合成N1,N3-di(pyridin-4-yl)isophthalamide (L7)…………………………….19
§ 2-1-3合成N1,N3,N5-tri(pyridin-3-yl)benzene-1,3,5- tricarboxamide (L11’)...........20
§ 2-2-1合成[ZnBr2(L6)2]n (1)......................................................................................21
§ 2-2-2合成[ZnI2(L6)]2 (2)…………………………………..............………………22
§ 2-2-3合成[ZnI2(L6)]n (3)..........................................................................................23
§ 2-2-4合成[Cd(OAc)2 (L6)2(H2O)]n (4).....................................................................23
§ 2-2-5合成[Cd(NO3)2(L6)3]n (5)................................................................................24
§ 2-2-6合成[ZnCl2(L7)2]n(6)………………………………………………………...25
§ 2-2-7合成[ZnBr2(L7)2]n(7).......................................................................................26
§ 2-2-8合成[ZnI2(L7)2]n(8)..........................................................................................27
§ 2-2-9合成[AgPF6(L11’)]n(9)....................................................................................28
第三章 結果與討論…………………………………...……………29
§ 3-1雙核超分子矩形的合成概念………………………………………………….29
§ 3-2化合物(1)~(3)的單晶結構……………………………………………………..29
§ 3-3化合物(4)~(5)的單晶結構……………………………………………………..34
§ 3-4化合物(6)~(8)的單晶結構……………………………………………………..38
§ 3-5化合物(9)的單晶結構…………………………………………………………42
§ 3-6-1化合物(1)、(2)的光譜探討………………………………………………….45
§ 3-6-2化合物(9)的光譜探討……………………………………………………….46
§ 3-7揮發性有機物質吸附的探討………………………………………………….47
§ 3-8結論…………………………………………………………………………….51
PART II : Photoinduced Electron Transfer (PET) Studies of Re(I) Complexes Containing 2-Pyridin-2-yl-1H- benzoimidazole and 2,2’-bis-(4,5-dimethylimidazole )
第一章 序論………………………………………………………….54
§ 1-1光誘導電子轉移簡介……………………………….…………………..…….54
第二章 合成………………………………………………...………..57
§ 2-1含錸金屬錯化合物的合成…………………………………………...………..57
§ 2-1-1合成[Re(CO)3Cl(py-bimH)](10)......................................................................57
§ 2-1-2合成Na[Re(CO)3Cl(py-bim)](11)...................................................................58
§ 2-1-3合成[Re(CO)3(NO3)(py-bimAuPPh3)](12)......................................................59
§ 2-1-4合成[Re(CO)3Cl(tm-bimH)](13).....................................................................60
§ 2-1-5合成[Na2Re(CO)3Cl(tm-bim)](14)..................................................................61
§ 2-1-6合成[Re(CO)3(NO3)(tm-bimAuPPh3)](15)......................................................62
第三章 結果與討論………………………………………………...63
§ 3-1錸金屬錯化合物(10)、(12)、(13)、(15)的單晶結構………………………..63
§ 3-2錸金屬錯化合物的光譜探討……………….…………………………………68
§ 3-2-1錸金屬錯化合物(10)~(13)的光譜探討……………………………………..68
§ 3-2-2溶劑效應探討………………………………………………………………..76
§ 3-3錸金屬錯化合物(13)~(15)的光譜探討………………………………………..80
§ 3-4結論…………………………………………………………………………….84
§ 3-5未來展望……………………………………………………………………….85

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