Porous Organic Cage Nanocrystals by Solution Mixing

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• 作者：Tom Hasell ; Samantha Y. Chong ; Kim E. Jelfs ; Dave J. Adams ; Andrew I. Cooper
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：January 11, 2012
• 年：2012
• 卷：134
• 期：1
• 页码：588-598
• 全文大小：1234K
• 年卷期：v.134,no.1(January 11, 2012)
• ISSN：1520-5126

文摘

We present here a simple method for the bottom-up fabrication of microporous organic particles with surface areas in the range 500鈥?000 m² g^鈥?. The method involves chiral recognition between prefabricated, intrinsically porous organic cage molecules that precipitate spontaneously upon mixing in solution. Fine control over particle size from 50 nm to 1 渭m can be achieved by varying the mixing temperature or the rate of mixing. No surfactants or templates are required, and the resulting organic dispersions are stable for months. In this method, the covalent synthesis of the cage modules can be separated from their solution processing into particles because the modules can be dissolved in common solvents. This allows a 鈥渕ix and match鈥?approach to porous organic particles. The marked solubility change that occurs upon mixing cages with opposite chirality is rationalized by density functional theory calculations that suggest favorable intermolecular interactions for heterochiral cage pairings. The important contribution of molecular disorder to porosity and surface area is highlighted. In one case, a purposefully amorphized sample has more than twice the surface area of its crystalline analogue.