High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages

Seung Bin Baek, Dohyun Moon, Robert Graf, Woo Jong Cho, Sung Woo Park, Tae Ung Yoon, Seung Joo Cho, In Chul Hwang, Youn Sang Bae, Hans W. Spiess, Hee Cheon Lee, Kwang S. Kim

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3 BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H3 BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.

Original languageEnglish
Pages (from-to)14156-14161
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume112
Issue number46
DOIs
Publication statusPublished - 2015 Nov 17

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Sorption
Gases
Molecules
Dimethylformamide
Synchrotrons
Temperature
Nuclear magnetic resonance
Single crystals
Magic angle spinning
Benzene
Powders
X ray powder diffraction
Hydrogen bonds
X ray diffraction
X rays
Crystals

All Science Journal Classification (ASJC) codes

  • General

Cite this

Baek, Seung Bin ; Moon, Dohyun ; Graf, Robert ; Cho, Woo Jong ; Park, Sung Woo ; Yoon, Tae Ung ; Cho, Seung Joo ; Hwang, In Chul ; Bae, Youn Sang ; Spiess, Hans W. ; Lee, Hee Cheon ; Kim, Kwang S. / High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages. In: Proceedings of the National Academy of Sciences of the United States of America. 2015 ; Vol. 112, No. 46. pp. 14156-14161.
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abstract = "Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3 BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H3 BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.",
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High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages. / Baek, Seung Bin; Moon, Dohyun; Graf, Robert; Cho, Woo Jong; Park, Sung Woo; Yoon, Tae Ung; Cho, Seung Joo; Hwang, In Chul; Bae, Youn Sang; Spiess, Hans W.; Lee, Hee Cheon; Kim, Kwang S.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 112, No. 46, 17.11.2015, p. 14156-14161.

Research output: Contribution to journalArticle

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AU - Baek, Seung Bin

AU - Moon, Dohyun

AU - Graf, Robert

AU - Cho, Woo Jong

AU - Park, Sung Woo

AU - Yoon, Tae Ung

AU - Cho, Seung Joo

AU - Hwang, In Chul

AU - Bae, Youn Sang

AU - Spiess, Hans W.

AU - Lee, Hee Cheon

AU - Kim, Kwang S.

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N2 - Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3 BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H3 BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.

AB - Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H3 BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H3 BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO2 with the organic framework and dynamic motion of CO2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO2 (a series of transient opening/closing of compartments enabling CO2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.

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