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研究生:莊仁翰
研究生(外文):Jen-HanChuang
論文名稱:多核銅(I)羧酸錯合物與含氮化合物間之機動自組裝
論文名稱(外文):Dynamic Self-Assembly of Multicopper (I) Carboxylate Complexes with Nitrogen-Containing Compounds
指導教授:許拱北許拱北引用關係
指導教授(外文):Kom-Bei Shiu
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:227
中文關鍵詞:自組裝組成機動超分子
外文關鍵詞:self-assemblydynamicsupramolecular chemistry
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[Cu2(µ-dppm2)(MeCN)2][BF4]2與含苯環的單羧酸 benzoic acid (BAc), o-toluic acid (oTAc), m-toluic acid (mTAc), p-toluic acid (pTAc), salicylic acid (Sac), 2-nitrobenzoic acid (2NBAc), 4-nitrobenzoic acid (4NBAc), 4-Phenylbutyric acid (4PBAc)及鄰, 間, 對苯二甲酸之雙羧酸 phthalic acid (PhAc), iso-phthalic acid (IsoPhAc), tere-phthalic acid (TerePhAc)反應形成 [Cu2(dppm)2(µ-BAc)](BF4) (1BF4), [Cu2(dppm)2(µ-oTAc)](BF4) (2BF4), [Cu2(dppm)2(µ-mTAc)](BF4) (3BF4), [Cu2(dppm)2(µ-pTAc)](BF4) (4BF4), [Cu2(dppm)2(µ-SAc)](BF4) (5BF4) , [Cu2(dppm)2(µ-4PBAc)](BF4) (6BF4), [Cu2(dppm)2(µ-2NBAc)](BF4) (7BF4), [Cu2(dppm)2(µ-4NBAc)](BF4) (8BF4), [{Cu2(dppm)2}2(µ-PhAc)](BF4)2 (9BF4)2 , [{Cu2(dppm)2}2(µ-IsoPhAc)](BF4)2 (10BF4)2 , [{Cu2(dppm)2}2(µ-TerephAc)](BF4)2 (11BF4)2
上述雙銅錯合物續與剛硬或柔軟的直線型雙芽含氮配位基N-N反應 (N-N = 4, 4’-bipyridyl (bipy) (a), 1, 2-bis (4-pyridyl)ethane (bpe) (b) , 1, 2-di (4-pyridyl)ethylene (dpe)(c), 4, 4’-trimethylenedipyridine (tmp) (d))形成多核銅錯合物,
包含寡聚物 {[Cu2(dppm)2(µ- BAc)]2(bpe)}(BF4)2, (1b(BF4) 2)
{[Cu2(dppm)2(µ-BAc)]2(dpe)}(BF4)2 (1c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(dpe)}(BF4)2 (2c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(bpe)}(BF4)2 (2b(BF4)2) ,
{[Cu2(dppm)2(µ-4PBAc)]2(bpe)}(BF4)2 (6b(BF4)2) ,
{[Cu2(dppm)2(µ-4NBAc)]2(bpe)}(BF4)2 (8b(BF4)2) ,
{[Cu2(dppm)2(µ-mTAc)]2(bpe)}(BF4)2 (3b(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(tmp)}(BF4)2 (2d(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(tmp)}(BF4)2 (4d(BF4)2) , {[Cu2(dppm)2(µ-Sac)]2(bpe)}(BF4)2 (5b(BF4)2) , {[Cu2(dppm)2(µ-2NBAc)]2(bpe)}(BF4)2 (7b(BF4)2) , {[Cu2(dppm)2(µ-pTAc)]2(bpe)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2(µ-2NBAc)]2(bipy)}(BF4)2 (7a(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(bipy)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2}2(µ-PhAc)2(bipy)}(BF4)4 (9a(BF4)4) ,
聚合物 [Cu2(dppm)2(µ-2NBAc)(tmp)]n(BF4)n (7d(BF4)n) ,
[Cu2(dppm)2(µ-BAc)(bipy)]n(BF4)n (1a(BF4)n) ,
[{Cu2(dppm)2}2(µ-PhAc)(bpe)]n(BF4)2n (9b(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(PhAc)(tmp)]n(BF4)2n (9d(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(IsoPhAc)(bipy)]n(BF4)2n (10a(BF4)2n)以及不規則金屬環 [{Cu2(dppm)2}2(µ-IsoPhAc)(bpe)](BF4)2 (10b(BF4)2) , [{Cu2(dppm)2}2(µ-IsoPhAc)(tmp)](BF4)2 (10d(BF4)2) 及長方形金屬環 {[[Cu2(dppm)2]2(µ-TerePhAc)]2(bpe)2}(BF4)4 (11b(BF4)4)
等結構。所有的錯合物,利用NMR、EA、IR、ESI-MS鑑定其性質,並且由X-ray data 得到固態結構。
藉由光譜及質譜的證據證明組成不同的超分子產物在溶劑中存在快速動力交換現象。[Cu2(dppm)2(µ-BAc)](BF4) 與tmp反應可以形成不同結構 [[Cu2(dppm)2(µ-BAc)]2(tmp)](BF4)2 (1d(BF4)2) 及 [{Cu2(dppm)2}(µ- BAc)(tmp)]n(BF4)n (1d(BF4)n)。

[Cu2(µ-dppm2)(MeCN)2][BF4]2 reacted with benzoic acid (BAc), o-toluic acid (oTAc), m-toluic acid (mTAc), p-toluic acid (pTAc), salicylic acid (Sac) , 2-nitrobenzoic acid (2NBAc), 4-nitrobenzoic acid (4NBAc), 4-Phenylbutyric acid (4PBAc), phthalic acid (PhAc), iso-phthalic acid (IsoPhAc), tere-phthalic acid (TerePhAc) to produced [Cu2(dppm)2(µ- BAc)](BF4) (1BF4), [Cu2(dppm)2(µ- oTAc)](BF4) (2BF4), [Cu2(dppm)2(µ- mTAc)](BF4) (3BF4), [Cu2(dppm)2(µ-p TAc)](BF4) (4BF4), [Cu2(dppm)2(µ-SAc)](BF4) (5BF4), [Cu2(dppm)2(µ-4PBAc)](BF4) (6BF4) , [Cu2(dppm)2(µ-2NBAc)](BF4) (7BF4) , [Cu2(dppm)2(µ-4NBAc)](BF4) (8BF4) , [{Cu2(dppm)2}2(µ-PhAc)](BF4)2 (9BF4)2 , [{Cu2(dppm)2}2(µ-IsoPhAc)](BF4)2 (10BF4)2 and[{Cu2(dppm)2}2(µ-TerephAc)] (BF4)2 (11BF4)2
then reacted with rigid or flexible linear bidentate donors, (N-N = 4, 4’-bipyridyl (bipy) (a), 1, 2-bis (4-pyridyl)ethane (bpe) (b) , 1, 2-di (4-pyridyl)ethylene (dpe)(c), 4, 4’-trimethylenedipyridine (tmp) (d)) , respectively . Twenty four compounds are formed,
including : oligomer{[Cu2(dppm)2(µ-BAc)]2(bpe)}(BF4)2 (1b(BF4)2) , {[Cu2(dppm)2(µ-BAc)]2(dpe)}(BF4)2 (1c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(dpe)}(BF4)2 (2c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(bpe)}(BF4)2 (2b(BF4)2) ,
{[Cu2(dppm)2(µ-4PBAc)]2(bpe)}(BF4)2 (6b(BF4)2) ,
{[Cu2(dppm)2(µ-4NBAc)]2(bpe)}(BF4)2 (8b(BF4)2) ,
{[Cu2(dppm)2(µ-mTAc)]2(bpe)}(BF4)2 (3b(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(tmp)}(BF4)2 (2d(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(tmp)}(BF4)2 (4d(BF4)2) , {[Cu2(dppm)2(µ-Sac)]2(bpe)}(BF4)2 (5b(BF4)2) , {[Cu2(dppm)2(µ-2NBAc)]2(bpe)}(BF4)2 (7b(BF4)2) , {[Cu2(dppm)2(µ-pTAc)]2(bpe)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2(µ-2NBAc)]2(bipy)}(BF4)2 (7a(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(bipy)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2}2(µ-PhAc)2(bipy)}(BF4)4 (9a(BF4)4) ,
polymer[Cu2(dppm)2(µ-2NBAc)(tmp)]n(BF4)n (7d(BF4)n) ,
[Cu2(dppm)2(µ- BAc)(bipy)]n(BF4)n (b(BF4)n) ,
[{Cu2(dppm)2}2(µ-PhAc)(bpe)]n(BF4)2n (9b(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(PhAc)(tmp)]n(BF4)2n (9d(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(IsoPhAc)(bipy)]n(BF4)2n (10a(BF4)2n) , irregular metallacycles [{Cu2(dppm)2}2(µ-IsoPhAc)(bpe)](BF4)2 (10b(BF4)2) , [{Cu2(dppm)2}2(µ-IsoPhAc)(tmp)](BF4)2 (10d(BF4) 2) and a rectangle
metallacyle {[[Cu2(dppm)2]2(µ-TerePhAc)]2(bpe)2}(BF4)4 (11b(BF4)4) .
All complexes were characterized by elemental analyses、 NMR 、ESI-MS and IR spectra . Single-crystal structures of each complex were also determined by X-ray single-crystal diffraction data.
Interestingly, in solution, both spectral and MS evidences for some
adducts show that rapid dynamic exchange exists between different supramolecules.Truly, one complex can form two different structures [[Cu2(dppm)2(µ- BAc)]2(tmp)](BF4) (1d(BF4)2) and [{Cu2(dppm)2}(µ- BAc)(tmp)]n(BF4)n (1d(BF4)n)。

摘要..........................................................I
Abstract.....................................................III
誌謝 .......................................................V
目錄.......................................................VII
表目錄................................................... VIII
附表目錄....................................................IX
圖目錄.....................................................X
附圖目錄...................................................XIII
第一章 緒論....................................................1
1-1 超分子化學...........................................1
1-2 機動化學.............................................4
1-3 文獻回顧............................................8
1-4 實驗動機.........................................16
第二章 實驗部分...............................................19
2-1實驗儀器/軟體與實驗操作............................19
2-2溶劑與藥品..........................................20
2-3 合成及鑑定.........................................21
(I) 單羧酸部份....................................32
(II) 雙羧酸部份....................................48
第三章 結果與討論.............................................55
(I)-1單羧酸單晶結構...................................55
(I)-2單羧酸的探討....................................75
(I)-3同組成不同比例晶體探討..........................82
(I)-4 溶液中的行為................. ...................85
(I)-4-(i) NMR的變溫實驗..... ..... ..... ..... .....85
(I)-4-(ii) ESI-MS.......................................87
(I)-5 反應機構預測...................................92
(II)-1雙羧酸晶體探討.................................93
(II)-2 雙羧酸系列的統整..............................113
第四章 結論..................................................114
參考文獻...................................................115
附錄....................................................116

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