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

DOI: 10.1038/ncomms14212 DOI Help

Authors: Zhenzhong Lu (University of Manchester) , Harry G. W. Godfrey (University of Manchester) , Ivan Da Silva (ISIS) , Yongqiang Cheng (Oak Ridge National Laboratory) , Mathew Savage (University of Manchester) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (University of Manchester) , Simon J. Teat (Advanced Light Source) , Kevin J. Gagnon (Advanced Light Source) , Mark D. Frogley (Diamond Light Source) , Pascal Manuel (ISIS) , Svemir Rudic , Anibal J. Ramirez-cuesta (Oak Ridge National Laboratory) , Timothy L. Easun (Cardiff University) , Sihai Yang (University of Manchester) , Martin Schröder (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Communications , VOL 8

State: Published (Approved)
Published: January 2017
Diamond Proposal Number(s): 13666

Open Access Open Access

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.

Journal Keywords: Metal–organic frameworks; Molecular self-assembly; Solid-state chemistry

Subject Areas: Chemistry, Materials


Instruments: B22-Multimode InfraRed imaging And Microspectroscopy

Other Facilities: Advanced Light Source

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