In Silico Prediction of Structural Properties of a Racemic Porous Organic Cage Crystal

Liu, Yang; Zhu, Guanghui; You, Wenqin; Tang, Hongjian; Jones, Christopher W.; Lively, Ryan P.; Sholl, David S.

doi:10.1021/acs.jpcc.8b08838

In Silico Prediction of Structural Properties of a Racemic Porous Organic Cage Crystal

Journal Article · Thu Dec 20 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b08838· OSTI ID:1566521

Liu, Yang ^[1]; Zhu, Guanghui ^[1]; You, Wenqin ^[1]; Tang, Hongjian ^[2]; Jones, Christopher W. ^[1]; ^[1]; ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Georgia Inst. of Technology, Atlanta, GA (United States); Southeast Univ., Jiangsu (China)

Porous organic cage (POC) solids are porous materials made up of individual porous molecules held together by noncovalent forces. While many examples of POCs have been made in homochiral forms (i.e., crystals in which every molecule has the same chirality), crystallization of POCs that contain mixtures of chiral molecules can also yield useful properties. For example, our previous work has demonstrated that a POC crystal [cage crystal 3 (CC3)-racemic] synthesized using a racemic mixture of diaminocyclohexane has improved sorption properties and stability than a similar POC crystal synthesized with homochiral diaminocyclohexane. The main purpose of this paper is to predict the structure of CC3-racemic with atomic detail because it is challenging to fully resolve the structure of this racemic crystal experimentally since only subtle differences exist between the racemic structure and the known crystal structure of homochiral CC3. Here, we introduce an in silico prediction method that combines electronic structure calculations and atomistic calculations to predict the structure of CC3-racemic. We first enumerate types of cage molecules that can be present in this material and establish their concentrations. A key observation from these calculations is that CC3-racemic is not made up of only CC3-R and CC3-S molecules and that an additional class of heterochiral cages is also present. By studying the packing energy of cage pairs in CC3-racemic, a lattice model representation of the racemic crystal is developed and used in MC simulations to assess the structure of extended crystals. By expanding the lattice model into atomic detail, fully detailed CC3-racemic crystal models are obtained. These models provide the most thorough description available to date of the composition and cage packing of this interesting material.

View Accepted Manuscript (DOE)

Research Organization:: Georgia Inst. of Technology, Atlanta, GA (United States); Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC)

Sponsoring Organization:: Dow Chemical Company; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012577

OSTI ID:: 1566521

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 3 Vol. 123; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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In Silico Prediction of Structural Properties of a Racemic Porous Organic Cage Crystal

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