A Robust Microporous Zinc Porphyrin Framework Solid

作者：Dennis W. Smithenry, Scott R. Wilson, Kenneth S. Suslick · 发表于：Inorganic Chemistry · 年份：2003 · DOI：10.1021/ic034873g · 被引用次数：117 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Porphyrin and Phthalocyanine Chemistry、Covalent Organic Framework Applications

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(4)O(6+) clusters, maintaining a charge-neutral framework. This cubic framework has 74% free volume and 4 x 7 A pores. N(2) adsorption gives a type I isotherm with a surface area of 800 m(2)/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.