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Title: Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [3] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. Univ. of Liverpool (United Kingdom). Dept. of Chemistry, Materials Innovation Factory
  2. Univ. of Southampton (United Kingdom). School of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 7; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1408449

Slater, Anna G., Reiss, Paul S., Pulido, Angeles, Little, Marc A., Holden, Daniel L., Chen, Linjiang, Chong, Samantha Y., Alston, Ben M., Clowes, Rob, Haranczyk, Maciej, Briggs, Michael E., Hasell, Tom, Day, Graeme M., and Cooper, Andrew I.. Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages. United States: N. p., Web. doi:10.1021/acscentsci.7b00145.
Slater, Anna G., Reiss, Paul S., Pulido, Angeles, Little, Marc A., Holden, Daniel L., Chen, Linjiang, Chong, Samantha Y., Alston, Ben M., Clowes, Rob, Haranczyk, Maciej, Briggs, Michael E., Hasell, Tom, Day, Graeme M., & Cooper, Andrew I.. Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages. United States. doi:10.1021/acscentsci.7b00145.
Slater, Anna G., Reiss, Paul S., Pulido, Angeles, Little, Marc A., Holden, Daniel L., Chen, Linjiang, Chong, Samantha Y., Alston, Ben M., Clowes, Rob, Haranczyk, Maciej, Briggs, Michael E., Hasell, Tom, Day, Graeme M., and Cooper, Andrew I.. 2017. "Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages". United States. doi:10.1021/acscentsci.7b00145. https://www.osti.gov/servlets/purl/1408449.
@article{osti_1408449,
title = {Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages},
author = {Slater, Anna G. and Reiss, Paul S. and Pulido, Angeles and Little, Marc A. and Holden, Daniel L. and Chen, Linjiang and Chong, Samantha Y. and Alston, Ben M. and Clowes, Rob and Haranczyk, Maciej and Briggs, Michael E. and Hasell, Tom and Day, Graeme M. and Cooper, Andrew I.},
abstractNote = {The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.},
doi = {10.1021/acscentsci.7b00145},
journal = {ACS Central Science},
number = 7,
volume = 3,
place = {United States},
year = {2017},
month = {6}
}