Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/14462
Title: Syntheses and characterizations of metal-organic frameworks with unusual topologies derived from flexible dipyridyl ligands
Authors: Wang, R
Han, L
Xu, L
Gong, Y
Zhou, Y
Hong, M
Chan, ASC
Keywords: Bridging ligands
Cadmium
Coordination polymers
X-ray diffraction
Zinc
Issue Date: 2004
Publisher: Wiley-VCH
Source: European journal of inorganic chemistry, 2004, v. , no. 18, p. 3751-3763 How to cite?
Journal: European journal of inorganic chemistry 
Abstract: Two flexible exo-bidentate ligands, 2,2′-bis(3-pyridylmethyleneoxy)- 1,1′-biphenylene (3,3′-bpp) and 2,2′-bis(4-pyridyl- methyleneoxy)-1,1′-biphenylene (4,4′-bpp), were synthesized and employed for the preparation of coordination polymers. Seven metal-organic complexes, [Zn 2(3,3′-bpp) 2Cl 4] (1), [Zn 2(3,3′-bpp) 2Br 4] (2), [Zn(4,4′-bpp)Cl 2] n (3), [Zn(4,4′-bpp)Br 2] n (4), [Co(4,4′-bpp) 2(SCN) 2] n (5), {[Cd(4,4′- bpp) 2(SCN) 2]·2H 2O} n (6) and [Cd(4,4′-bpp) (dca) 2] n (7) (dca - = dicyanamide), have been obtained through self-assembly reactions of 3,3′-bpp or 4,4′-bpp with the divalent metal ions Zn II, Co II and Cd II. Crystal structure analyses reveal that 1 and 2 are dinuclear metallomacrocycles, are isomorphous and possess a layer network built from metallomacrocycles through π-π interactions. In drastic contrast, 3 and 4 exhibit a three-dimensional structure consisting of one-dimensional polymeric chains held together through π-π interactions between adjacent pyridyl rings. The metal-organic frameworks of 5, 6, and 7 possess unusual topologies: Complex 5 is a two-dimensional polymer based on folded rectangular boxes and zigzag chains, whereas 6 is a polycatenated species consisting of inclined interpenetrating two-dimensional layers, and each layer is constructed by the alternating assembly of left-hand (M) and right-hand (P) cylindrical 2j helices. In 7, dca - connects Cd II centers forming a two-dimensional {Cd(dca) 2} n layer, which is fused with (M)- and (P)-Cd-(4,4′-bpp) helical chains into a three-dimensional structure. The results suggest that the nature of organic ligands and the coordination preferences of transitional metal ions have a great influence on the structures of metal-organic complexes.
URI: http://hdl.handle.net/10397/14462
ISSN: 1434-1948
EISSN: 1099-0682
DOI: 10.1002/ejic.200400173
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