Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework View Full Text


Ontology type: schema:ScholarlyArticle      Open Access: True


Article Info

DATE

2017-02-13

AUTHORS

Zhenzhong Lu, Harry G. W. Godfrey, Ivan da Silva, Yongqiang Cheng, Mathew Savage, Floriana Tuna, Eric J. L. McInnes, Simon J. Teat, Kevin J. Gagnon, Mark D. Frogley, Pascal Manuel, Svemir Rudić, Anibal J. Ramirez-Cuesta, Timothy L. Easun, Sihai Yang, Martin Schröder

ABSTRACT

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, =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 ···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. More... »

PAGES

14212

Identifiers

URI

http://scigraph.springernature.com/pub.10.1038/ncomms14212

DOI

http://dx.doi.org/10.1038/ncomms14212

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1083802580

PUBMED

https://www.ncbi.nlm.nih.gov/pubmed/28194014


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