TY - JOUR
T1 - A computational study of enantioselective adsorption in a homochiral metal-organic framework
AU - Bao, Xiaoying
AU - Broadbelt, Linda J.
AU - Snurr, Randall Q.
N1 - Funding Information:
We thank the National Science Foundation (CTS-0507013) for financial support. We also thank TeraGrid for the computational resources under project no. TG-CTS080016N.
PY - 2009/1
Y1 - 2009/1
N2 - The potential application of a homochiral metal-organic framework (MOF) made from cadmium corners and BINOL-type linkers for enantioselective separations of chiral hydrocarbons was investigated using grand canonical Monte Carlo simulations. Adsorption of racemic mixtures of (R,S)-1,3-dimethyl-1,2- propadiene, (R,S)-1,2-dimethylcyclobutane and (R,S)-1,2-dimethylcyclopropane was simulated. The results show that an enantiomeric excess (ee) of over 50% can be achieved for 1,3-dimethyl-1,2-propadiene, while more moderate ee values were observed for the cyclic compounds. The adsorption sites, diastereomeric complexes and adsorption energies were analysed to understand the enantioselective adsorption. It is shown that the small zigzag pores of the homochiral MOF account primarily for the enantioselective adsorption, whereas the larger helical pores show almost no enantioselectivity. The results also demonstrate that both intrinsic enantioselectivity and accessibility of the adsorption sites are important for the overall enantioselective separation.
AB - The potential application of a homochiral metal-organic framework (MOF) made from cadmium corners and BINOL-type linkers for enantioselective separations of chiral hydrocarbons was investigated using grand canonical Monte Carlo simulations. Adsorption of racemic mixtures of (R,S)-1,3-dimethyl-1,2- propadiene, (R,S)-1,2-dimethylcyclobutane and (R,S)-1,2-dimethylcyclopropane was simulated. The results show that an enantiomeric excess (ee) of over 50% can be achieved for 1,3-dimethyl-1,2-propadiene, while more moderate ee values were observed for the cyclic compounds. The adsorption sites, diastereomeric complexes and adsorption energies were analysed to understand the enantioselective adsorption. It is shown that the small zigzag pores of the homochiral MOF account primarily for the enantioselective adsorption, whereas the larger helical pores show almost no enantioselectivity. The results also demonstrate that both intrinsic enantioselectivity and accessibility of the adsorption sites are important for the overall enantioselective separation.
KW - Enantioselective adsorption
KW - GCMC
KW - Metal-organic frameworks
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U2 - 10.1080/08927020802422064
DO - 10.1080/08927020802422064
M3 - Article
AN - SCOPUS:61549125008
VL - 35
SP - 50
EP - 59
JO - Molecular Simulation
JF - Molecular Simulation
SN - 0892-7022
IS - 1-2
ER -