ic800422g_si_001.cif (171.75 kB)

Multi-Dimensional Transition-Metal Coordination Polymers of 4,4′-Bipyridine-N,N′-dioxide: 1D Chains and 2D Sheets

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posted on 06.10.2008, 00:00 by Junhua Jia, Alexander J. Blake, Neil R. Champness, Peter Hubberstey, Claire Wilson, Martin Schröder
Reaction of 4,4′-bipyridine-N,N-dioxide (L) with a variety of transition-metal salts in MeOH affords a range of coordination polymer products. For the complexes [FeCl3(μ-L)], 1, and ([Cu(L)2(OHMe)2(μ-L)]·2PF6·n(solv)), 2, 1D chain structures are observed, whereas ([Mn(μ-L)3]·2ClO4), 3, and ([Cu(μ-L)3]·2BF4), 4, both show 2D sheet architectures incorporating an unusual 36-hxl topology. The more common 44-sql topology is observed in [Cd(ONO2)2(μ-L)2], 5, ([Cu(OHMe)2(μ-L)2]·2ZrF5), 6, ([Cu(L)2(μ-L)2]·2EF6) (7 E = P; 8 E = Sb), and ([Et4N][Cu(OHMe)0.5(μ-L)2(μ-FSiF4F)0.5]·2SbF6·n(solv)), 9. In 6, the [ZrF5] anion, formed in situ from [ZrF6]2−, forms 1D anionic chains ([ZrF5]) of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated ([Cu(OHMe)2(μ-L)2]2+) 44-sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 44-sql sheets of stoichiometry ([Cu(L)2]2+) coordinatively linked by bridging [SiF6]2− anions to give a structure of 5-c 44.66-sqp topology. The mononuclear [Cu(L)6]·2BF4 (10) and [Cd(L)6]·2NO3 (11) and binuclear complexes [(Cu(L)(OH2))2(μ-L)2)]·2SiF6·n(solv), 12, are also reported. The majority of the coordination polymers are free of solvent and are nonporous. Thermal treatment of materials that do contain solvent results in structural disintegration of the complex structures giving no permanent porosity.