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Smithenry, Dennis W.
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article
A Robust Microporous Zinc Porphyrin Framework Solid
Abstract
<p>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 Zn<sub>4</sub>O<sup>6+</sup> clusters, maintaining a charge-neutral framework. This cubic framework has 74% free volume and 4 x 7 Å pores. N<sub>2</sub> adsorption gives a type I isotherm with a surface area of 800 m<sup>2</sup>/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.</p>