A Robust Microporous Zinc Porphyrin Framework Solid

A robust microporous zinc(II) metalloporphyrin framework solid has been synthesized. The proposed structural model developed from X-ray single crystal data has an interpenetrated three-dimensional framework of zinc trans-biscarboxylate tetraarylporphyrins whose carboxylates coordinate the six edges of tetrahedral Zn4O6+ clusters, maintaining a charge-neutral framework. This cubic framework has 74% free volume and 4 × 7 Å pores. N2 adsorption gives a type I isotherm with a surface area of 800 m2/g, which is greater than that of a typical zeolite. Experimental evidence indicates that the interpenetrated frameworks of the evacuated solid remain intact and retain a microporous structure. This is a versatile framework system: alteration of the metal in the porphyrin may create a catalytically active solid, and modification of the 10-, 20-substituents of the porphyrin can provide control over both the polarity and the size of the pores.