Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework
| Autor: | Lu, Zhenzhong, Godfrey, Harry G. W., da Silva, Ivan, Cheng, Yongqiang, Savage, Mathew, Tuna, Floriana, McInnes, Eric J. L., Teat, Simon J., Gagnon, Kevin J., Frogley, Mark D., Manuel, Pascal, Rudic, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, Schröder, Martin |
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| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: | |
| Zdroj: | Nature Communications, Vol 8, Iss 1, Pp 1-10 (2017) Nature communications, vol 8, iss 1 Lu, Z; Godfrey, HGW; Da Silva, I; Cheng, Y; Savage, M; Tuna, F; et al.(2017). Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. Nature Communications, 8. doi: 10.1038/ncomms14212. Lawrence Berkeley National Laboratory: Retrieved from: http://www.escholarship.org/uc/item/9h1322n3 Lu, Z, Godfrey, H, Da Silva, I, Cheng, Y, Savage, M, Tuna, F, Mcinnes, E, Teat, S J, Gagnon, K J, Frogley, M D, Manuel, P, Rudić, S, J. Ramirez-Cuesta, A, Easun, T L, Yang, S & Schroder, M 2017, ' Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework ', Nature Communications, vol. 8, 14212 . https://doi.org/10.1038/ncomms14212 |
| ISSN: | 2041-1723 |
| DOI: | 10.1038/ncomms14212. |
| Popis: | Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g−1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, OH... OCO2 =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique OCO2···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites. |
| Databáze: | OpenAIRE |
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