Multi-dimensional transition-metal coordination polymers of 4,4'-bipyridine-N,N'-dioxide: 1D chains and 2D sheets

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 FeCl 3(mu-L)] infinity, 1, and (Cu(L) 2(OHMe) 2(mu-L)].2PF 6. n(solv)) infinity, 2, 1D chain structures are observed, whereas (Mn(mu-L) 3].2ClO 4) infinity, 3, and (Cu(mu-L) 3].2BF 4) infinity, 4, both show 2D sheet architectures incorporating an unusual 3 (6)- hxl topology. The more common 4 (4)- sql topology is observed in Cd(ONO 2) 2(mu-L) 2] infinity, 5, (Cu(OHMe) 2(mu-L) 2].2ZrF 5) infinity, 6, (Cu(L) 2(mu-L) 2].2EF 6) infinity ( 7 E = P; 8 E = Sb), and (Et 4N]Cu(OHMe) 0.5(mu-L) 2(mu-FSiF 4F) 0.5].2SbF 6. n(solv)) infinity, 9. In 6, the ZrF 5] (-) anion, formed in situ from ZrF 6] (2-), forms 1D anionic chains (ZrF 5] (-)) infinity of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated (Cu(OHMe) 2(mu-L) 2] (2+)) infinity 4 (4)- sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 4 (4)- sql sheets of stoichiometry (Cu(L) 2] (2+)) infinity coordinatively linked by bridging SiF 6] (2-) anions to give a structure of 5-c 4 (4).6 (6)- sqp topology. The mononuclear Cu(L) 6].2BF 4 ( 10) and Cd(L) 6].2NO 3 ( 11) and binuclear complexes (Cu(L)(OH 2)) 2(mu-L) 2)].2SiF 6. 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.