Four new 2D porous polymeric frames from the self-assembly of silver triflate and silver tosylate with free-base and Zn-metallated 5,10,15,20-tetra(4-pyridyl)porphyrin

The reactions of 5,10,15,20-tetra(4-pyridyl) porphyrin (H(2)Tpyp) and its Zn-metallated derivative (ZnTpyp) with Ag-I triflate and Ag-I tosylate have produced four new 2D coordination polymers, namely [(AgTrif)(2)(H(2)Tpyp)] . xSolv (1), [(Ag{m-Chla}(2))(2)(H(2)Tpyp)](Tos)(2) . xSolv (2), [Ag-2(m-Tol)(ZnTpyp)(2)](Trif)(2) . xSolv (3) and [(AgTos)(2)(ZnTpyp . DMA)] . xSolv (4) ( Trif = triflate, Tos = tosylate, m-Chla = m-chloroaniline, m-Tol = m-toluidine, DMA = N, N-dimethylacetamide). Compounds 1 and 4 consist of (4,4) layers of large square meshes, with the porphyrin units as corners and the silver ions as digonal spacers. Compound 2 has the same ( 4,4) topology but the layers are highly undulated due to the tetrahedral coordination geometry of the silver spacers, that are connected to two pyridyl groups and to two m-chloroaniline molecules. In 3 the 2D motifs are complex thick layers formed both from the self-coordination of Zn(II)Tpyp units via axial bonding of Zn-II ions with pyridyl groups of adjacent molecules and from the coordination of pyridyl groups to silver ions. Compounds 1 - 4 contain free voids ( range 23 - 42% of the cell volume) full of disordered solvent molecules. A brief analysis of the known networks assembled with H(2)Tpyp or M(II)Tpyp building blocks is also reported.