Smithenry Dennis W, Wilson Scott R, Suslick Kenneth S
School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, Illinois 61801, USA.
Inorg Chem. 2003 Dec 1;42(24):7719-21. doi: 10.1021/ic034873g.
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.
一种坚固的微孔锌（II）金属卟啉骨架固体已被合成。根据X射线单晶数据建立的结构模型显示，其具有相互贯穿的三维锌反式双羧酸四芳基卟啉骨架，其中羧酸盐与四面体Zn(4)O(6+)簇的六条边配位，维持电荷中性骨架。这种立方骨架具有74%的自由体积和4×7 Å的孔。N(2)吸附给出I型等温线，表面积为800 m(2)/g，大于典型沸石的表面积。实验证据表明，抽空固体的相互贯穿骨架保持完整并保留微孔结构。这是一个多功能的骨架体系：卟啉中金属的改变可能产生催化活性固体，卟啉10-、20-位取代基的修饰可以控制孔的极性和大小。
