pH Dependent Structural Diversity of Metal Complexes with 5-(4H-1,2,4-Triazol-4-yl)benzene-1,3-dicarboxylic Acid
详细信息 查看全文
- 作者：Min Chen ; Shui-Sheng Chen ; Taka-aki Okamura ; Zhi Su ; Man-Sheng Chen ; Yue Zhao ; Wei-Yin Sun ; Norikazu Ueyama
- 刊名：Crystal Growth & Design
- 出版年：2011
- 出版时间：May 4, 2011
- 年：2011
- 卷：11
- 期：5
- 页码：1901-1912
- 全文大小：1283K
- 年卷期：v.11,no.5(May 4, 2011)
- ISSN：1528-7505
文摘
A ligand 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L) with N- and O-donors was successfully applied to construct a series of coordination complexes [Cu3(渭3-OH)2(HL)4]n (1), [Co(HL)2(H2O)4]路3H2O (2), [Ni(HL)2(H2O)4]路3H2O (3), [Mn(HL)2]n (4), {[Cu2(L)2(渭-OH2)2]路3H2O}n (5), {[Co2(L)2(渭-OH2)2]路3H2O}n (6), {[Ni2(L)2(渭-OH2)2]路3H2O}n (7), and {[Mn(L)(渭-OH2)]路2H2O}n (8) under hydrothermal conditions. By adjusting the reaction pH, H2L ligand is partially deprotonated to give HL鈥?/sup> form in 1鈥?b>4 and completely deprotonated to afford L2鈥?/sup> form in 5鈥?b>8. The structural analyses revealed that complex 1 is a three-dimensional (3D) (3,3,5,6)-connected framework with Point (Schl盲fli) symbol of (4.6.8)2(42.65.83)2(42.66.86.10)(42.6)2, while 2 and 3 are discrete mononuclear complexes which are extended by hydrogen bonds to form 3D frameworks. The (3,6)-connected 3D framework of 4 is defined as a metal鈥搊rganic replica of anatase (ant) net with Point (Schl盲fli) symbol of (42.6)2(44.62.88.10). Complexes 5鈥?b>7 are isostructural and display (4,5)-connected 3D frameworks with Point (Schl盲fli) symbol of (42.52.62)(42.53.62.73), and 8 is a binodal (4,6)-connected 3D net with the Point (Schl盲fli) symbol of (3.54.6)(32.56.66.9). The results revealed that the reaction pH and the metal center play important role in determining the structures of the complexes. Magnetic studies indicate that the mixed 渭3-hydroxo and triazolyl bridges in 1 and the double syn鈥?i>syn carboxylate bridges in 4 mediate antiferromagnetic interactions. The alternating triazolyl and water bridges show alternating ferro- and antiferromagnetic interactions in 5 but antiferromagnetic interactions in 6 and 7. The mixed triazolyl and water bridges show antiferromagnetic interactions in 8.