Chiral porous solids: Adsorption and preparation strategy from molecular simulation

COLL 494

Louis A. Clark1, Shaji Chempath2, and Randall Q. Snurr2. (1) Department of Bioengineering, University of California, Berkeley, CA 94720, (2) Department of Chemical Engineering, Northwestern University, 2145 Sheridan Road, E-136, Evanston, IL 60208
A scheme is proposed for the transformation of certain achiral porous solids into chiral solids. At least two materials with racemic mixtures of chiral pores are now available. The UCSB-7 materials and the beta type zeolite have pores that can be described as mixtures of opposite-handed helices. Molecular simulations indicate that enantiomers of some molecules adsorb predominantly in pores of a distinct handedness. Subsequent oligomerization of these molecules would block one of two pore types and yield a solid with exploitable chirality. Adsorption simulations indicate that sizable segregation of tight-fitting racemic mixtures occurs. For example, when isomers of 1,2-dimethyl-cyclobutane are adsorbed in UCSB-7 at 300K a potential energy difference of 4.6 kJ/mol leads to a composition in one pore that is approximately 3/4 of one racemate and 1/4 of the other. Simulations allow us to examine other potential selective pore-blockers and their relative placement in the two solids, as well as their diffusion rates.
 

Chiral Surfaces

Division of Colloid and Surface Chemistry
The 225th ACS National Meeting, New Orleans, LA, March 23-27, 2003