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

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. ORCID: https://orcid.org/0000-0002-0713-2642, Yang, Sihai and Schröder, Martin 2017. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. Nature Communications 8 , 14212. 10.1038/ncomms14212

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Nature Research
ISSN:	2041-1723
Funders:	EPSRC, ERC and University of Manchester
Date of First Compliant Deposit:	14 February 2017
Date of Acceptance:	5 December 2016
Last Modified:	05 May 2023 11:39
URI:	https://orca.cardiff.ac.uk/id/eprint/98302

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