Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD
CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/141059 |
| _version_ | 1826209735308738560 |
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| author | Oppenheim, Julius J Mancuso, Jenna L Wright, Ashley M Rieth, Adam J Hendon, Christopher H Dincǎ, Mircea |
| author_facet | Oppenheim, Julius J Mancuso, Jenna L Wright, Ashley M Rieth, Adam J Hendon, Christopher H Dincǎ, Mircea |
| author_sort | Oppenheim, Julius J |
| collection | MIT |
| description | CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption. |
| first_indexed | 2024-09-23T14:28:12Z |
| format | Article |
| id | mit-1721.1/141059 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T14:28:12Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1410592022-03-09T03:10:53Z Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD Oppenheim, Julius J Mancuso, Jenna L Wright, Ashley M Rieth, Adam J Hendon, Christopher H Dincǎ, Mircea CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption. 2022-03-08T14:16:42Z 2022-03-08T14:16:42Z 2021 2022-03-08T14:07:32Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/141059 Oppenheim, Julius J, Mancuso, Jenna L, Wright, Ashley M, Rieth, Adam J, Hendon, Christopher H et al. 2021. "Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD." Journal of the American Chemical Society, 143 (40). en 10.1021/JACS.1C07449 Journal of the American Chemical Society Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf American Chemical Society (ACS) MIT web domain |
| spellingShingle | Oppenheim, Julius J Mancuso, Jenna L Wright, Ashley M Rieth, Adam J Hendon, Christopher H Dincǎ, Mircea Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title | Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title_full | Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title_fullStr | Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title_full_unstemmed | Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title_short | Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal–Organic Framework Ni 2 X 2 BTDD |
| title_sort | divergent adsorption behavior controlled by primary coordination sphere anions in the metal organic framework ni 2 x 2 btdd |
| url | https://hdl.handle.net/1721.1/141059 |
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