含對稱型2-胺基-5-鹵素嘧啶配位基或非對稱型甲基, 4-(5-鹵素嘧啶基-2-醯胺基)苯甲酸酯配位基與一價銀錯化合物之合成、結構與性質之探討

本論文包含三個部分，主要探討含2-胺基-5-鹵素嘧啶配位基及其衍生物之一價銀鹽類錯化合物的合成、結構與分子間之作用力。本文所探討之所有化合物均利用元素分析儀、紅外線光譜儀、紫外線-可見光光譜儀、螢光分析儀與熱重分析儀分析鑑定之，並利用單晶X-ray繞射儀鑑定結構。在第一部份中，以L1 (L1 = 2-胺基-5-氯嘧啶)、L2 (L2 = 2-胺基-5-溴嘧啶)或L3 (L3 = 2-胺基-5-碘嘧啶)配位基與一價銀鹽類反應，可得到一系列的錯化合物[Ag(L1)(NO3)]42H2O, 12H2O, [Ag(L1)(ClO4)]∞, 2, [Ag(L1)(BF4)(CH3OH)]∞, 3, [Ag(L2)(BF4)(CH3OH)]∞, 4, {[Ag(L2)(SbF6)](C4H10O)1.25}∞, 51.25C4H10O, [Ag(L1)2](CF3SO3), 6, [Ag(L2)2](CF3SO3), 7, [Ag(L3)(CF3SO3)]∞, 8, {[Ag(L1)(CF3SO3)](C4H8O)}6, 96C4H8O, {[Ag(L2)(CF3SO3)](C4H10O)}6, 106C4H10O and {[Ag(L3)(CF3SO3)](C4H8O)}6, 116C4H8O。四核錯化合物1為一16–membered金屬巨環結構。錯化合物2與5則為具有不同的螺旋週期的一維螺旋鏈狀結構。一維Z字鏈化合物3與4皆利用Ag---X作用力形成二維層狀結構。同晶形的錯化合物6與7皆為單核結構。錯化合物8則為一維Z字鏈結構透過強的C-I---Ag作用力進而形成三維的超分子結構。而錯化合物9、10與11皆由六個銀離子與六個配位基自組裝形成一24–membered金屬巨環結構。在第二部份中，利用新型的甲基,4-(嘧啶基-2-醯胺基)苯甲酸酯配位基, L4與ㄧ價銀鹽類反應，可得到一系列的錯化合物{[Ag(L4)](NO3)}∞, 12, {[Ag(L4)(CF3SO3)](C4H8O)0.25}∞, 130.25C4H8O, [Ag(L4)2](X), (X = ClO4, 14; X = BF4, 15; X = PF6, 16; X = SbF6, 17)。錯化合物12與13為一維鏈狀結構，其配位基採用三芽的配位型式且無Ag---Ag作用力。錯化合物14到17皆形成單核結構，其配位基採用雙芽的配位型式並且有Ag---Ag作用力。而當其陰離子為較大的八面體時，其Ag---Ag之間的距離則越長，反之當陰離子為較小的四面體時，則其距離較短。在第三部份中，利用所合成出三種新型的甲基,4-(5-鹵素嘧啶基-2-醯胺基)苯甲酸酯配位基 (鹵素 =氯, L5; 鹵素 = 溴, L6; 鹵素 = 碘, L7)與一價銀鹽類反應，可得到一系列錯化合物[Ag2(L5)(NO3)2]∞, 18, [Ag2(L6)(NO3)2]∞, 19, [Ag(L7)(NO3)]∞, 20, [Ag(L5)(X)]∞ (X = CF3SO3, 21; X = ClO4, 24), [Ag(L6)(X)]∞ (X = CF3SO3, 22; X = ClO4, 25), [Ag(L7)(X)]∞ (X = CF3SO3, 23; X = ClO4, 26), [Ag(L5)3](BF4), 27, [Ag(L6)3](BF4), 28, [Ag(L7)3](ClO4)•C4H8O, 29C4H8O, {[Ag(L6)](BF4)•(C4H8O)0.5}∞, 300.5C4H8O, [Ag2(L7)4](X)2, (X = BF4, 31; X = PF6, 32; X = SbF6, 33)。化合物18、19與30皆形成二維層狀高分子。其中化合物18、19為具有{4;6;8}{4;62;83}{62;8}的拓譜構型，而化合物30為具有{4;62}2{42;62;82}的拓譜構型。化合物20到26皆為一維的高分子結構。其中化合物20為直線鏈狀結構，化合物21、22與26為Z字鏈狀結構，而化合物23、24與25則為螺旋鏈狀結構。化合物27、28與29皆為單核錯化合物但其金屬配位中心的幾何構型變化從三角稜柱到四面體因而形成不同的三維超分子結構。化合物31、32與33皆為雙核之錯化合物結構，然而只有在32與33中觀察到C-I---I-C的作用力，可能是由於陰離子大小的影響。

關鍵字

一價銀錯化合物； 2-胺基-5-鹵素嘧啶；甲基4-(5-鹵素嘧啶基-2-醯胺基)苯甲酸酯

並列摘要

This thesis includes three parts discussing the syntheses, structures and intermolecular interactions of Ag(I) complexes containing halopyrimidyl ligands. All complexes have been characterized by IR, UV-vis and FL spectroscopic methods, EA and TGA analysis and single-crystal X-ray diffraction. In the part I, a series of Ag(I) complexes derived from 2-amino-5-chloropyrimidine, L1, 2-amino-5-bromopyrimidine, L2 and 2-amino-5-iodopyrimidine, L3 have been successfully accomplished. The reaction of AgNO3 with L1 in CH3CN produced complex [Ag(L1)(NO3)]42H2O, 12H2O. [Ag(L1)(ClO4)]∞, 2 was prepared by reaction of L1 with AgClO4 in MeOH. The reactions of L1 and L2 with AgBF4 in MeOH afforded the complexes [Ag(L1)(BF4)(CH3OH)]∞, 3 and [Ag(L2)(BF4)(CH3OH)]∞, 4, respectively. {[Ag(L2)(SbF6)](C4H10O)1.25}∞, 51.25C4H10O, was prepared by reaction of L2 with AgSbF6 in MeOH. The complexes [Ag(L1)2](CF3SO3), 6, [Ag(L2)2](CF3SO3), 7 and [Ag(L3)(CF3SO3)]∞, 8 were prepared by reaction of L1, L2 and L3 with AgCF3SO3 in THF, respectively. The reaction of L1, L2 and L3 with AgCF3SO3 in THF reflux afforded the {[Ag(L1)(CF3SO3)](C4H8O)}6, 96C4H8O, {[Ag(L2)(CF3SO3)](C4H10O)}6, 106C4H10O and {[Ag(L3)(CF3SO3)](C4H8O)}6, 116C4H8O. The cations of the tetranuclear complex 1 form the sixteen–membered metallocycles. Complexes 2 and 5 show the 1-D helical chains with different lengths of the repeating units. The 1-D zigzag chains for 3 and 4 are also interlinked through the Ag---X interactions (X = Cl in 3; X = Br in 4) to form 2-D molecular sheets. The cations of the isomorphous complexes 6 and 7 are mononuclear. The cations of the complex 8 form 1-D zigzag chains and the iodine atoms of pyrimidyl rings coordinate to the silver atoms through strong C-I---Ag interactions, resulting in a 3-D framework. The complexes 9, 10 and 11 show cyclic self-assembly of six Ag(Ι) atoms and six ligands, resulting in twenty-four membered metallocycles. In the part II, The new ligand methyl, 4-(pyrimidin-2-ylcarbamoyl)benzoate, L4, has been synthesized and a series of the complexes have been prepared by reaction with Ag(I) salts. The 1-D polymeric chains {[Ag(L4)](NO3)}∞, 12 and {[Ag(L4)(CF3SO3)](C4H8O)0.25}∞, 130.25C4H8O were prepared by the reactions of L4 with AgNO3 in MeOH and AgCF3SO3 in THF solution systems, respectively. The mononuclear complexes [Ag(L4)2](X), (X = ClO4, 14; X = BF4, 15; X = PF6, 16; X = SbF6, 17) were prepared by the reactions of L4 with Ag(I) salts in MeOH. Complexes 12 and 13 show 1-D linear chains with the ligands adopted as tridentate mode and no Ag---Ag interaction was observed. In the mononuclear complexes 14 – 17, the L4 ligands adopt as bidentate mode and Ag---Ag interaction was formed. The Ag---Ag distances of the complexes with the larger, octahedral anions, are significantly longer than that those with the smaller, tetrahedral anions. In the part III, Three new ligands of the type methyl, 4-(5-halopyrimidin-2-ylcarbamoyl)benzoate (halo = chloro, L5; halo = bromo, L6; halo = iodo, L7) have been synthesized and a series of the complexes have been prepared by reaction with Ag(I) salts. The 2-D polymeric sheets [Ag2(L5)(NO3)2]∞, 18 and [Ag2(L6)(NO3)2]∞, 19, were prepared by reaction of L5 and L6 with AgNO3 in MeOH. The reaction of L7 with AgNO3 afforded the 1-D polymeric chain [Ag(L7)(NO3)]∞, 20. The reactions of L5, L6 and L7 with AgCF3SO3 and AgClO4 in THF solution systems afforded the 1-D polymers [Ag(L5)(X)]∞ (X = CF3SO3, 21; X = ClO4, 24), [Ag(L6)(X)]∞ (X = CF3SO3, 22; X = ClO4, 25) and [Ag(L7)(X)]∞ (X = CF3SO3, 23; X = ClO4, 26), respectively. The complexes [Ag(L5)3](BF4), 27, [Ag(L6)3](BF4), 28 and [Ag(L7)3](ClO4)•C4H8O, 29•C4H8O were prepared by reaction of L5 and L6 with AgBF4 and L7 with AgClO4 in THF, respectively. The reaction of L6 with AgBF4 in THF afforded the 2-D polymeric network {[Ag(L6)](BF4)•(C4H8O)0.5}∞, 30•0.5C4H8O. The complexes [Ag2(L7)4](X)2, (X = BF4, 31; X = PF6, 32; X = SbF6, 33) were prepared by reaction of L7 with Ag(I) salts in MeOH. Complexes 18 and 19 are 2-D polymers with a {4;6;8}{4;62;83}{62;8} topology, while complex 30 shows a 2-D polymer with a {4;62}2{42;62;82} topology. In the 1-D polymeric complexes 20 − 26, the complex 20 shows a 1-D linear chain, the complexes 21, 22 and 26 show the 1-D zigzag chains, and the complexes 23, 24 and 25 show the 1-D helical chains. The mononuclear complexes 27, 28 and 29 show different coordination geometries from trigonal prismatic to tetrahedral to form different 3-D supramolecular frameworks. Complexes 31, 32 and 33 show dimeric structures, while the C-I---I-C interactions were only observed in 32 and 33.

並列關鍵字

2-Amino-5-halopyrimidine ； Methyl4-(5-halopyrimidin-2-ylcarbamoyl)benzoate ； silver complexes

參考文獻

3 (a) P. Ayyappan, O. R. Evans, Y. Cui, K. A. Wheeler and W. Lin, Inorg. Chem. 2002, 41, 4978; (b) B.-H. Ye, M.-L. Tong and X.-M. Chen, Coord. Chem. Rev., 2005, 249, 545; (c) A. Y. Robin and K. M. Fromm, Coord. Chem. Rev., 2006, 250, 2127; (d) S. Leininger, B. Olenyuk and P. J. Stang, Chem. Rev., 2000, 100, 853.

25 (a) G. R. Desiraju and T. Steiner, The Weak Hydrogen Bond in Structural Chemistry and Biology; Oxford University Press: Oxford, 1999; (b) M. D. Prasanna and T. N. Guru Row, Crystal Eng., 2000, 3, 135; (c) B. K. Saha, R. K. R. Jetti, L. S. Reddy, S. Aitipamula and A. Nangia, Cryst. Grwoth Des., 2005, 5, 887; (b) Y. X. Lu, J. W. Zou, Y. H. Wang and Q. S. Yu, J. Chem. Phys., 2007, 1, 334; (e) D. Schollmeyer, O. V. Shishkin, T. Rühl and M. O. Vysotsky, Cryst. Eng. Commun. 2008, 10, 715; (f) S. J. Lee, K.-M. Park, K. Yang and Y. Kang, Inorg. Chem., 2009, 48, 1030; (g) F. C. Pigge V. R. Vangala, D. C. Swenson and N. P. Rath, Cryst. Grwoth Des. 2010, 10, 224.

13 (a) L. Carlucci, G. Ciani, D. M. Proserpio and A. Sironi, Angew. Chem., Int. Ed., 1995, 34, 1895; (b) L. Carlucci, G. Ciani, F. Porta, D. M. Proserpio and L. Santagostini, Angew. Chem., Int. Ed., 2002, 41, 1907; (c) L. Carlucci, G. Ciani, D. M. Proserpio and S. Rizzato, Chem. Eur. J., 2002, 8, 1520; (d) M. Pascu, F. Tuna, E. Kolodziejczyk, G. I. Pascu, G. Clarkson and M. J. Hannon, J. Chem. Soc., Dalton Trans., 2004, 1546; (e) A. Galet, M. C. Muňoz, A. B. Gaspar and J. A. Real, Inorg. Chem., 2005, 44, 8749; (f) M. Kondracka and U. Englert, Inorg. Chem., 2008, 47, 10246; (g) I. A. Baburin, V. A. Blatov, L. Carlucci, G. Ciani and D. M. Proserpio, Cryst. Growth Des., 2008, 8, 519; (h) G. Huang, C.-K. Tsang, Z. Xu, K. Li, M. Zeller, A. D. Hunter, S. S.-Y. Chui and C.-M. Che, Cryst. Growth Des., 2009, 9, 1444.

20 Bondi, J. Phys. Chem., 1964, 68, 441.

21 F. Zordan, L. Brammer and P. J. Sherwood, J. Am. Chem. Soc., 2005, 127, 5979.

國際替代計量

含對稱型2-胺基-5-鹵素嘧啶配位基或非對稱型甲基, 4-(5-鹵素嘧啶基-2-醯胺基)苯甲酸酯配位基與一價銀錯化合物之合成、結構與性質之探討

未授權

主題瀏覽