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 (H2Tpyp) and its Zn-metallated derivative (ZnTpyp) with AgI triflate and AgI tosylate have produced four new 2D coordination polymers, namely [(AgTrif)2(H2Tpyp)]·xSolv (1), [(Ag{m-Chla}2)2(H2Tpyp)](Tos)2·xSolv (2), [Ag2(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 ZnIITpyp units via axial bonding of ZnII 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 H2Tpyp or MIITpyp building blocks is also reported.