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Title: Crossover Sorption of C₂H₂/CO₂ and C₂H₆/C₂H₄ in Soft Porous Coordination Networks
Authors: Shivanna, Mohana
Otake, Ken-ichi
Hiraide, Shotaro  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0001-7853-1619 (unconfirmed)
Fujikawa, Takao
Wang, Ping
Gu, Yifan
Ashitani, Hirotaka
Kawaguchi, Shogo
Kubota, Yoshiki
Miyahara, Minoru T.
Kitagawa, Susumu  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0001-6956-9543 (unconfirmed)
Author's alias: 大竹, 研一
平出, 翔太郎
藤川, 鷹王
宮原, 稔
北川, 進
Keywords: C₂H₂/CO₂ and C₂H₆/C₂H₄ Sorption
Crossover Sorption
Flexibility
In-Situ Characterization
Porous Coordination Polymer
Issue Date: 25-Sep-2023
Publisher: Wiley
Journal title: Angewandte Chemie International Edition
Volume: 62
Issue: 39
Thesis number: e202308438
Abstract: Porous sorbents are materials that are used for various applications, including storage and separation. Typically, the uptake of a single gas by a sorbent decreases with temperature, but the relative affinity for two similar gases does not change. However, in this study, we report a rare example of “crossover sorption, ” in which the uptake capacity and apparent affinity for two similar gases reverse at different temperatures. We synthesized two soft porous coordination polymers (PCPs), [Zn₂(L1)(L2)₂]n (PCP-1) and [Zn₂(L1)(L3)₂]n (PCP-2) (L1= 1, 4-bis(4-pyridyl)benzene, L2=5-methyl-1, 3-di(4-carboxyphenyl)benzene, and L3=5-methoxy-1, 3-di(4-carboxyphenyl)benzene). These PCPs exhibits structural changes upon gas sorption and show the crossover sorption for both C₂H₂/CO₂ and C₂H₆/C₂H₄, in which the apparent affinity reverse with temperature. We used in situ gas-loading single-crystal X-ray diffraction (SCXRD) analysis to reveal the guest inclusion structures of PCP-1 for C₂H₂, CO₂, C₂H₆, and C₂H₄ gases at various temperatures. Interestingly, we observed three-step single-crystal to single-crystal (sc-sc) transformations with the different loading phases under these gases, providing insight into guest binding positions, nature of host–guest or guest-guest interactions, and their phase transformations upon exposure to these gases. Combining with theoretical investigation, we have fully elucidated the crossover sorption in the flexible coordination networks, which involves a reversal of apparent affinity and uptake of similar gases at different temperatures. We discovered that this behaviour can be explained by the delicate balance between guest binding and host–guest and guest-guest interactions.
Rights: This is the peer reviewed version of the following article: [Shivanna, M., Otake, K.-i., Hiraide, S., Fujikawa, T., Wang, P., Gu, Y., Ashitani, H., Kawaguchi, S., Kubota, Y., Miyahara, M. T., Kitagawa, S., Angew. Chem. Int. Ed. 2023, 62, e202308438.], which has been published in final form at https://doi.org/10.1002/anie.202308438. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
The full-text file will be made open to the public on 21 August 2024 in accordance with publisher's 'Terms and Conditions for Self-Archiving'.
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
URI: http://hdl.handle.net/2433/285163
DOI(Published Version): 10.1002/anie.202308438
PubMed ID: 37534579
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