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

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

doi:10.1038/ncomms14212

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

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

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81 Scopus citations

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(V^III) {[V^III ₂ (OH)₂ (L)], LH₄ =biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V^IV), [V^IV ₂ O₂ (L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V^III) 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(V^IV) shows CO₂ bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique O_CO2 ···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.

Original language	English
Article number	14212
Journal	Nature Communications
Volume	8
DOIs	https://doi.org/10.1038/ncomms14212
State	Published - Feb 13 2017

Funding

We thank EPSRC, ERC and University of Manchester for funding. We thank EPSRC for funding of the UK National EPR Facility at Manchester. We are especially grateful to STFC and the ISIS Neutron Facility for access to the Beamlines TOSCA and WISH, to Diamond Light Source for access to Beamline B22, to the Advanced Light Source for access to Beamline 11.3.1 and to ORNL for access to Beamline VISION. The computing resources were made available through the VirtuES (Virtual Experiments in Spectroscopy) project, funded by Laboratory Directed Research and Development program (LDRD 7739) at the Oak Ridge National Laboratory. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The development of the gas cell used in this work was partially funded by the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0001015.

Funders	Funder number
VirtuES
U.S. Department of Energy	DE-AC02-05CH11231
Office of Science
Basic Energy Sciences	DE-SC0001015
Oak Ridge National Laboratory
Laboratory Directed Research and Development	LDRD 7739
Horizon 2020 Framework Programme	742401
Engineering and Physical Sciences Research Council
Science and Technology Facilities Council
University of Manchester
European Research Council

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Lu, Z., Godfrey, H. G. W., Da Silva, I., Cheng, Y., Savage, M., Tuna, F., McInnes, E. J. L., Teat, S. J., Gagnon, K. J., Frogley, M. D., Manuel, P., Rudić, S., Ramirez-Cuesta, A. J., Easun, T. L., Yang, S., & Schröder, M. (2017). Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. Nature Communications, 8, Article 14212. https://doi.org/10.1038/ncomms14212

@article{cf02748e949644788c518c1defd334ed,

title = "Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework",

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) {[VIII 2 (OH)2 (L)], LH4 =biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV 2 O2 (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) {\AA}. 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) {\AA}]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.",

author = "Zhenzhong Lu and Godfrey, {Harry G.W.} and {Da Silva}, Ivan and Yongqiang Cheng and Mathew Savage and Floriana Tuna and McInnes, {Eric J.L.} and Teat, {Simon J.} and Gagnon, {Kevin J.} and Frogley, {Mark D.} and Pascal Manuel and Svemir Rudi{\'c} and Ramirez-Cuesta, {Anibal J.} and Easun, {Timothy L.} and Sihai Yang and Martin Schr{\"o}der",

note = "Publisher Copyright: {\textcopyright} 2017 The Author(s).",

year = "2017",

month = feb,

day = "13",

doi = "10.1038/ncomms14212",

language = "English",

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Lu, Z, Godfrey, HGW, Da Silva, I, Cheng, Y, Savage, M, Tuna, F, McInnes, EJL, Teat, SJ, Gagnon, KJ, Frogley, MD, Manuel, P, Rudić, S, Ramirez-Cuesta, AJ, Easun, TL, Yang, S & Schröder, 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

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T1 - Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

AU - Lu, Zhenzhong

AU - Godfrey, Harry G.W.

AU - Da Silva, Ivan

AU - Cheng, Yongqiang

AU - Savage, Mathew

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Teat, Simon J.

AU - Gagnon, Kevin J.

AU - Frogley, Mark D.

AU - Manuel, Pascal

AU - Rudić, Svemir

AU - Ramirez-Cuesta, Anibal J.

AU - Easun, Timothy L.

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2017/2/13

Y1 - 2017/2/13

N2 - 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) {[VIII 2 (OH)2 (L)], LH4 =biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV 2 O2 (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 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.

AB - 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) {[VIII 2 (OH)2 (L)], LH4 =biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV 2 O2 (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 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.

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U2 - 10.1038/ncomms14212

DO - 10.1038/ncomms14212

M3 - Article

C2 - 28194014

AN - SCOPUS:85012293330

SN - 2041-1723

VL - 8

JO - Nature Communications

JF - Nature Communications

M1 - 14212

ER -

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

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