title: Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance.
abstract: Both known and new CC3-based porous organic cages are prepared and exposed to acidic SO2 in vapor and liquid conditions. Distinct differences in the stability of the CC3 cages exist depending on the chirality of the diamine linkers used. The acid catalyzed CC3 degradation mechanism is probed via in situ IR and a degradation pathway is proposed and supported with computational results. CC3 crystals synthesized with racemic mixtures of diaminocyclohexane exhibited enhanced stability compared to CC3-R and CC3-S. Confocal fluorescent microscope images reveal that the stability difference in CC3 species originates from an abundance of mesoporous grain boundaries in CC3-R and CC3-S, allowing facile access of aqueous SO2 throughout the crystal, promoting decomposition. These grain boundaries are absent from CC3 crystals made with racemic linkers.
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Guanghui
authors.initials: G
authors.lastname: Zhu
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Christopher D
authors.initials: CD
authors.lastname: Hoffman
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Yang
authors.initials: Y
authors.lastname: Liu
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Souryadeep
authors.initials: S
authors.lastname: Bhattacharyya
authors.affiliation: Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, 37831, USA.
authors.forename: Uma
authors.initials: U
authors.lastname: Tumuluri
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Melinda L
authors.initials: ML
authors.lastname: Jue
authors.affiliation: Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, 37831, USA.
authors.forename: Zili
authors.initials: Z
authors.lastname: Wu
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: David S
authors.initials: DS
authors.lastname: Sholl
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Sankar
authors.initials: S
authors.lastname: Nair
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA.
authors.forename: Christopher W
authors.initials: CW
authors.lastname: Jones
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332, USA. ryan.lively@chbe.gatech.edu.
authors.forename: Ryan P
authors.identifier: http://orcid.org/0000-0002-8039-4008
authors.initials: RP
authors.lastname: Lively
keywords: acid gas interactions; cage compounds; grain boundaries; microporous materials; sulfur dioxide