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姓名 吳艾芸(Ai-Yun Wu) 查詢紙本館藏 畢業系所 化學學系 論文名稱 含苯咪唑三芽基之鈷、鋅、鎘金屬配位聚合物之自組裝合成、結構與性質探討
(Self-Assembly, Structures and Properties of Tripodal Benzimidazoyl-Containing Co(II), Zn(II), and Cd(II) Metal–Organic Frameworks)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 本論文主旨為研究1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6- trimethylbenzene (TBzIm)搭配不同羧酸根配子及鈷、鋅、鎘二價金屬離子之水浴自組裝合成反應,共合成五種配位聚合物,並研究得到的配位聚合物之結構與性質,本論文分成三部分探討。
(一)利用有機配子TBzIm和4-aminobenzoic acid (4-abc)與鎘金屬離子,進行水浴自組裝反應,得到配位聚合物1。以有機配子TBzIm和4-abc與CdCl2•2.5H2O反應,於80 °C下反應得到化合物{[Cd5Cl10(TBzIm)4]•2H2O}n (1),化合物1為三維孔洞結構,且孔道中含有規律排列的客分子水。結構中經由特殊的五核鎘做為結構單元,再經由TBzIm橋接此結構單元形成無限擴張的三維結構。在此結構中有機配子TBzIm為文獻中少見的intermediate構型,苯咪唑上的苯環為向內收縮形式。若是不加入4-abc亦可得到此化合物,只是晶形為細針狀較不易解晶。
(二)使用TBzIm搭配鋅金屬離子或鈷金屬離子,混合剛性羧酸基2,6-naphthalenedicarboxylic acid (2,6-ndc)或1,4-naphthalenedicarboxylic acid (1,4-ndc)進行水浴自組裝反應,得到配位聚合物2?3。以有機配子TBzIm和 2,6-ndc與Zn(NO3)2‧6H2O反應,於80 °C下反應得到化合物{[Zn3(TBzIm)2(2,6-ndc)3]•5DMF•5H2O}n (2);以有機配子TBzIm和 1,4-ndc與CoCl2‧6H2O反應,於80 °C下反應得到化合物{[Co3Cl2(TBzIm)2(1,4-ndc)2]}n (3),所得到的化合物皆為三維pillared-layer structure。其中化合物3結構中TBzIm為文獻中少見的intermediate構型,苯咪唑上的苯環為向內形式。
(三)使用TBzIm搭配dimethylmalonic acid (dmm)以及鈷金屬離子,進行水浴自組裝反應,得到配位聚合物4?5。以有機配子TBzIm和dmm與Co(C2H3O2)2•4H2O反應,在80 °C下反應得到化合物{[Co3(TBzIm)3(dmm)2(HCO2)][HCO2]•8H2O}n (4);若是將反應濃度減半,同樣以有機配子TBzIm和dmm與Co(C2H3O2)2•4H2O反應,在80 °C下反應得到化合物{[Co3(TBzIm)2(dmm)3]•2DMF•H2O}n (5),化合物4?5皆為二維層狀結構,兩者反應中,雖然比例相同,但因濃度不同,反應速度與晶體成長速度也不同,因此得到不同結構的產物。
摘要(英) In this thesis, metal–organic coordination frameworks were prepared by reacting a ligand, 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm), with Co2+, Zn2+, Cd2+ and different carboxylate ligands under 80 °C conditions. The synthetic method, structures and physical properties of these compounds were investigated.
We report five compounds in this study, {[Cd5Cl10(TBzIm)4]•2H2O}n (1), {[Zn3(TBzIm)2(2,6-ndc)3]•5DMF•5H2O}n (2), {[Co3Cl2(TBzIm)2(1,4-ndc)2]}n (3), {[Co3(TBzIm)3(dmm)2(HCO2)][HCO2]•8H2O}n (4), {[Co3(TBzIm)2(dmm)3]•2DMF•H2O}n (5). A semi-rigid tripodal ligand, TBzIm, was first reacted with CdCl2•2.5H2O and 4-aminobenzoic acid (4-abc) to afford Compound 1 under 80 °C conditions. Compound 1 is comprised of a 3D porous metal–organic framework,which is built up from pentanuclear Cd2+ center repeating units. The pore of compound 1 is contains guest water molecules. In this case, TBzIm remains in a rare intermediate conformation.
In the second part, TBzIm was reacted with different metal ions and carboxylate ligands (2,6-naphthalenedicarboxylic acid, 2,6-ndc and 1,4-naphthalenedicarboxylic acid, 1,4-ndc) to afford a two 3D pillar-layer structure at a temperature of under 80 °C. Compound 2 was produced from the self-assembly of TBzIm, Zn(NO3)2•6H2O, and 2,6-ndc. Compound 3 was prepared from TBzIm, CoCl2•6H2O, and 1,4-ndc. TBzIm remains in a rare intermediate conformation in the compound 3.
In the third part, TBzIm was reacted with Co(C2H3O2)2•4H2O and dimethylmalonic acid (dmm) to produce a two layered structure at a temperature of under 80 °C. Compound 4 was prepared from TBzIm, Co(C2H3O2)2•4H2O, and dmm. The concentration of reactants is different between compounds 4 and compound 5. The concentration of compound 5 is doubled that for compound 4. The steric hindrance of TBzIm play important roles in the architectural engineering between these two crystals.
關鍵字(中) ★ 自組裝
★ 1、3、5-三(苯咪唑-1-基甲基)-2、4、6-三甲基苯
★ 金屬-有機配位聚合物關鍵字(英) ★ tripodal benzimidazoyl
★ self-assembly
★ metal–organic frameworks論文目次 摘要 i
ABSTRACT iii
誌謝 iv
目錄 vi
圖目錄 viii
表目錄 xiii
第一章 緒論 1
1-1 前言 1
1-2 超分子化學(Supramolecular chemistry) 2
1-3 自組裝合成法(Self-assembly method)21-24 10
1-4 配位聚合物 (Coordination polymer) 16
第二章 實驗設計概念與文獻回顧 24
2-1配位聚合物的設計概念 24
第三章 實驗部分 29
3-1儀器與藥品 29
3-1-1 儀器 29
3-1-2 藥品 30
3-2配子與化合物合成 31
3-2-1 有機配子1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm)之合成 31
3-2-2 第一部分: 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm)與鎘金屬鹽類之合成 32
3-2-3 第二部份: 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm)與金屬鹽類混合剛性羧酸基之合成 32
3-2-4 第三部份: 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (TBzIm)與鈷金屬鹽類之合成 33
第四章 結果與討論 35
4-1化合物{[Cd5Cl10(TBzIm)4]•2H2O}n (1)之合成與結構描述及其性質分析: 35
4-2化合物{[Zn3(TBzIm)2(2,6-ndc)3]•5DMF•5H2O}n(2)之合成與結構描述及其性質分析: 44
4-3化合物{[Co3Cl2(TBzIm)2(1,4-ndc)2]}n (3)之合成與結構描述及其性質分析: 52
4-4化合物{[Co3(TBzIm)3(dmm)2(HCO2)][HCO2]•8H2O}n (4)之合成與結構描述及其性質分析: 59
4-5化合物{[Co3(TBzIm)2(dmm)3]•2DMF•H2O}n (5)之合成與結構描述及其性質分析: 68
第五章 結論 72
參考文獻 73
附錄 76
參考文獻 [1] Millward, A. R.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 17999.
[2] Hou, Z. J.; Liu, L.; Xu, L.; Xu, Z.; Wang, W.; Li, F.; Ye, M. Chem. Mater. 1999, 11, 3177.
[3] (a) Perkin, K. K.; Turner, J. L.; Wooley, K. L.; Mann, S. Nano Lett. 2005, 5, 1457. (b) Jung, Y. J.; Kar, S.; Talapatra, S.; Soldano, C.; Viswanathan, G.; Li, X.; Yao, Z.; Ou, F. S.; Avadhanula, A.; Vajtai, R.; Curran, S.; Nalamasu, O.; Ajayan, P. M. Nano Lett. 2006, 6, 413. (c) Luechinger, N. A.; Loher, S.; Athanassiou, E. K.; Grass, R. N.; Stark, W. J. Langmuir 2007, 3473.
[4] (a) Yan, X.; Liu, G.; Haeussler, M.; Tang, B. Z. Chem. Mater. 2005, 17, 6053. (b)
Shi, J. M.; Sun, Y. M.; Zhang, X.; Yi, L.; Cheng, P.; Liu, L. D. J. Phys. Chem. A 2006, 110, 7677. (c) Lawandy, M. A.; Huang, X.; Wang, R. J.; Li, J.; Lu, J. Y. Inorg. Chem. 1999, 38, 5410.
[5] Lehn, J. M. Supramolecular Chemistry : Concepts and Perspectives; VCH, New
York. 1995.
[6] Lehn, J. M. PNAS 2002, 99, 4763.
[7] Christoph, J. J. Chem. Soc., Dalton. Trans. 2000, 3885.
[8] Jonathan, W. S.; Jerry, L. A. Supramolecular Chemistry; Wiley, New York 2000.
[9] (a) Lie, Y.; Li, G.; Li, X.; Cui, Y. Angew. Chem. Int. Ed. 2007, 46, 6301. (b)
Dinca, M.; Long, J. R. J. Am. Chem. Soc. 2007, 129, 11172.
[10](a) Kondo, A.; Noguchi, H.; Kajiro, H.; Carlucci, L.; Mercandelli, P.; Proserpio, D. M.; Tanaka, H.; Kaneko, K.; Kanoh, H. Phys. Chem. B. 2006, 110, 25565. (b) Wang, F. Q.; Zheng, X. J.; Wan, Y. H.; Sun, C. Y.; Wang, Z. M.; Wang, K. Z.; Jin, L. P. Inorg. Chem. 2007, 46, 2956. (c) Llabres i Xamena, F. X.; Corma, A.; Garcia, H. J. Phys. Chem. C 2007, 111, 80.
[11]Aakeroy, C. B.; Beatty, A. M.; Lorimer, K. R. J. Chem. Soc., Dalton Trans. 2000, 3869.
[12]Mazik, M.; Blaser, D.; Boese, R. Chem. Eur. J. 2001, 6, 2865.
[13]Tadokoro, M.; Shiomi, T.; Isobe, K.; Nakasuji, K. Nakasuji, K. Inorg. Chem.
2001, 40, 5467.
[14] Prior, T. J.; Rosseinsky, M. J. Chem. Commun. 2001, 1222.
[15] Lehn, J. M. Scienec 1985, 227,849.
[16] Pure & Appi. Chem. 1978, 50, 871.
[17] Fischer, E. Ber. Deutsch. Chem. Ges. 1894, 27, 2985.
[18] Wells, A. F. in Structural Inorganic Chemistry, Oxford University Press, London, 5th edn, 1984.
[19] http://cst-www.nrl.navy.mil/lattice/struk.picts/b1.s.png
[20] Etler, M. C. Acc. Chem. Res. 1990, 23, 220-238.
[21]李光華, 化學 (Chemistry, The Chinese Chem. Soc. Taipei) 1994, 52, 405.
[22] Fajita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc. 1994, 116,
1151.
[23] West, A. R. Solid State Chemistry and it’s Applications. John Wiley & Son Ltd.
Singapore, 1984.
[24] Raberau, A. Angew. Chem. Int, Ed. Engl. 1985, 24, 1026.
[25] Rajesh, C.; Partha, S. M.; Peter, J. S. Chem. Rev. 2011, 111, 6810-6918.
[26] Li, J.-R.; Julian, S.; Zhou, H.-C. Chem. Rev. 2012, 112, 869-932.
[27] Li, J.-R.; Ryan, J. K.; Zhou, H.-C. Chem. Soc. Rev. 2009, 38, 1477-1504.
[28] Norbert, S.; Shyam, B. Chem. Rev. 2012, 112, 933-969.
[29] Kitagawa, S.; Uemera, K. Chem. Soc. Rev. 2005, 34, 109-119..
[30] Ockwig, N. W.; Friedrichs, O. D.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2005, 38, 176-182.
[31] (a) Kitagawa, S.; Kondo, M. Bull. Chem. Soc. Jpn. 1998, 71, 1739. (b) Hannon, M. J.; Painting, C. L.; Plummer, E. A.; Childs, L. J.; Alcock, N. W. Chem. Eur. J. 2002, 8, 2225.
[32] (a)Bu, X.-H.; Chen, W.; Lu, S.-L.; Zhang, R.-H.; Liao, D.-Z.; Bu, W.-M.;
Shionoya, M.; Brisse, F.; Ribas, J. Angew. Chem. Int. Ed. 2001, 40, 3201. (b) Bu, X.-H.; Weng, W.; Du, M.; Chen, W.; Li, J. R.; Zhang, R. H.; Zhao, L. J. Inorg. Chem. 2002, 41, 1007.
[33] (a) Noveron, J. C.; Lah, M. S.; Sesto, R. E. D.; Arif, A. M.; Miller, J. S.; Stang, P. J. J. Am. Chem. Soc. 2002, 124, 6613. (b) Xu, F. B.; Li, Q. S.; Zeng, X. S.; Leng, X.B.; Zhang, Z. Z. Organometallics 2004, 23, 632
[34] (a) Su, C. Y.; Goforth, A. M.; Smith, M. D.; zur Loye, H. C. Inorg. Chem. 2003, 42, 5685. (b) Su, C. Y.; Smith, M. D.; zur Loye, H. C. Angew. Chem. Int. Ed. 2003, 42, 4085. (c) Chi, K. W.; Addicott, C.; Kryschenko,Y. K.; Stang, P. J. J. Org. Chem. 2004, 69, 964. (d) Chi, K. W.; Addicott, C.; Stang, P. J. J. Org. Chem. 2004, 69, 2910.
[35] (a) Su, C. Y.; Cai, Y. P.; Chen, C. L.; Zhang, H. X.; Kang, B. S. J. Chem. Soc., Dalton Trans. 2001, 359. (b) Su, C. Y.; Cai, Y. P.; Chen, C. L.; Smith, M. D.; Kaim, W.; zur Loye, H. C. J. Am. Chem. Soc. 2003, 125, 8595.
[36] Steel, P. J. Acc. Chem. Res. 2005, 38, 243.
[37] Wu, J. Y.; Lin, Y. F.; Chuang, C. H.; Tseng, T. W.; Wen, Y. S.; Lu, K. L. Inorg. Chem. 2008, 47, 10349.
[38] Addison, A. W.; Rao, T. N.; Reedijk, J.; Rijn, J. V.; Verschoor, G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.
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