Copper(I) and silver(I) coordination frameworks involving extended bipyridazine bridges

1,4-(Pyridazin-4-yl) benzene (bpph), a new N-donor tetradentate ligand, was prepared by inverse electron demand cycloaddition reacting 1,4-diethynylbenzene and 1,2,4,5-tetrazine. In combination with Cu(I) and Ag(I) ions, it affords coordination framework topologies that were dominated by assembly of dinuclear metal-pyridazine secondary building blocks'' [M-2(mu-pdz)(2)] supporting further polymeric connectivity. In structures [Cu-2(bpph)(CH3CN)(2){S2O6}] (1) and [Ag-6(bpph)(3)(H2O)(6){C6H4(COO)(2)}(2)]C6H4(COO)(2)center dot 4H(2)O (8) interconnection of the dinuclear nodes occurs with anionic dithionate and isophthalate bridges, while [Ag-2(bpph){C6H5CO2}(2)]center dot 2H(2)O (7) adopts a linear chain structure incorporating disilver(I) pyridazine units and terminal benzoate anions. [Cu-4(bpph)(5)](BF4)(4)center dot 4CHCl(3) (2) has a 3D supramolecular structure involving polycatenation of the 2D bilayer'' metal-organic topologies built up of five-connected dinuclear nodes. Frameworks of [Ag(bpph){NO3}]center dot CHCl3 (3) and [Ag(bpph){C2F5COO}] (5) exist as 2D square-grids nets supported with sets of tetra- and bidentate bipyridazine bridges, while closely related [Ag-4(bpph)(3){CF3COO}(4)]center dot CH3CN (4) is a 1D ladder'' polymer. The three-fold interpenetrated 3D diamondoid framework of [Ag-4(bpph)(3){CH3SO3}(4)]center dot 2CHCl(3) (6) was based upon more complicated tetranuclear nodes [Ag-4(mu-pdz)(4)(pdz)(2)].