Ancillary Ligands Dependent Structural Diversity of A Series of Metal鈥揙rganic Frameworks Based on 3,5-Bis(3-carboxyphenyl)pyridine

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• 作者：Liming Fan ; Xiutang Zhang ; Zhong Sun ; Wei Zhang ; Yuanshuai Ding ; Weiliu Fan ; Liming Sun ; Xian Zhao ; Han Lei
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：June 5, 2013
• 年：2013
• 卷：13
• 期：6
• 页码：2462-2475
• 全文大小：1039K
• 年卷期：v.13,no.6(June 5, 2013)
• ISSN：1528-7505

文摘

A series of novel multidimensional transition metal鈥搊rganic frameworks (MOFs), [Cu(Hbcpb)₂]_n (1), [Co(bcpb)]_n (2), [Co(Hbcpb)₂(1,4-bib)]n (3), {[M(bcpb)(1,4-bimb)]路xH₂O}n (M = Co (4), Cu (5), Ni (6), x = 1 for 5, 2 for 4 and 6), [Co(bcpb)(4,4鈥?bibp)]_n (7), {[Co(bcpb)(4,4鈥?bibp)]路2H₂O}_n (8), and [Ni₂(bcpb)₂(4,4鈥?bimbp)₂]_n (9), were synthesized under hydrothermal conditions in the presence of N-donor ancillary ligands [H₂bcpb = 3,5-bis(3-carboxyphenyl)pyridine, 1,4-bib = 1,4-bis(1H-imidazol-4-yl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-ylmethyl)benzene, 4,4鈥?bibp = 4,4鈥?bis(imidazol-1-yl)biphenyl, 4,4鈥?bimbp = 4,4鈥?bis(imidazol-1-ylmethyl)biphenyl]. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. By adjusting the reaction pH, the H₂bcpb ligand is partially deprotonated to give the Hbcpb^{鈥?/sup> form in 1 and 3, and completely deprotonated to afford the bcpb2鈥?/sup> form in 2 and 4鈥?b>9. Complex 1 exhibits a two-dimensional (2D) (3,6)-connected kgd topology with the Schl盲fli symbol of (43)₂(46路66路83). The three-dimensional (3D) framework of 2 is defined as a (4,4)-connected pts topology with the Schl盲fli symbol of (42路84). Complex 3 displays a (4,6)-connected pcu topology with the Schl盲fli symbol of (412路63) built from 44 2D nets with the help of 1,4-bib. Complexes 4鈥?b>6 are isomorphism and show a 3D (3,5)-connected mbm framework with the Point Schl盲fli symbol of (4路62)(4路66路83). The supramolecular isomers of 7 and 8, resulted from the different pH in the reaction, exhibit (3,5)-connected (42路67路8)(42路6) 3,5-L2 and (4,6)-connected (44路610路8)(44路62) fsc topology, respectively. Complex 9 can be regard as an unprecedented (3,5)-connected 3D 3,5-T1 frameworks with the point Schl盲fli symbol of (42路65路83)(42路6). The results revealed that the crystal architectures and the coordination modes of H₂bcpb are attributed to the factors, including metal cations, pH, and the N-donor ancillary ligands.}