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Porous Organic Cage Nanocrystals by Solution Mixing

DOI: 10.1021/ja209156v DOI Help

Authors: Tom Hasell (University of Liverpool) , Sam Chong (University of Liverpool) , Kim E. Jelfs (University of Liverpool) , Dave Adams (University of Liverpool) , Andrew I Cooper (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 134 (1) , PAGES 588 - 598

State: Published (Approved)
Published: November 2011
Diamond Proposal Number(s): 7040

Abstract: We present here a simple method for the bottom-up fabrication of microporous organic particles with surface areas in the range 500–1000 m2 g–1. 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 ?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 “mix and match” 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.

Journal Keywords: Porous Organic Materials

Subject Areas: Chemistry, Materials


Instruments: I11-High Resolution Powder Diffraction

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