Ameliorated synthetic methodology for crystalline lanthanoid-metalloporphyrin open frameworks based on a multitopic octacarboxy-porphyrin scaffold: structural, gas sorption and photophysical properties

New crystalline lanthanoid-metalloporphyrin porous frameworks [(Zn(H 2 O)-OCPP)Ln 2 (H 2 O) 4 Na 2 ] n ·solvent (Ln = Sm, Eu, Gd, Tb, and Dy) (LnMPF-1) were synthesized from an octatopic tetrakis-(3,5-dicarboxyphenyl)porphyrin building block through a synthetic approach using NaOH as a modulator to enhance the robustness of the metal-organic-framework (MOF) product and the formation of sizeable crystals. The formulated MOFs adopt a (4,8)-connected topology and are perforated by 1D tubular zigzag channels of about 1.5 nm in diameter. The frameworks possess permanent porosity and display appealing photophysical properties. A novel synthetic methodology has been applied to obtain sizeable single crystals of wide-pore porphyrin-based MOFs.