Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework

Zhenzhong Lu; Harry Godfrey; Ivan Da Silva; Yongqiang Cheng; Mathew Savage; Floriana Tuna; Eric Mcinnes; Simon J. Teat; Kevin J. Gagnon; Mark D. Frogley; Pascal Manuel; Svemir Rudić; Anibal J. Ramirez-Cuesta; Timothy L. Easun; Sihai Yang; Martin Schroder

doi:10.1038/ncomms14212

Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework

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

Research output: Contribution to journal › Article › peer-review

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^III₂(OH)₂(L)], LH₄=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V^IV), [V^IV₂O₂(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, OH... O_CO2 =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
Early online date	13 Feb 2017
DOIs	https://doi.org/10.1038/ncomms14212
Publication status	Published - 2017

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CCDC 1481146: Experimental Crystal Structure Determination
Lu, Z. (Contributor), Godfrey, H. (Contributor), Da Silva, I. (Contributor), Cheng, Y. (Contributor), Savage, M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Teat, S. J. (Contributor), Gagnon, K. J. (Contributor), Frogley, M. D. (Contributor), Manuel, P. (Contributor), Rudić, S. (Contributor), J. Ramirez-Cuesta, A. (Contributor), Easun, T. L. (Contributor), Yang, S. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lq7xg, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lq7xg&sid=DataCite
Dataset
CCDC 1481144: Experimental Crystal Structure Determination
Lu, Z. (Contributor), Godfrey, H. (Contributor), Da Silva, I. (Contributor), Cheng, Y. (Contributor), Savage, M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Teat, S. J. (Contributor), Gagnon, K. J. (Contributor), Frogley, M. D. (Contributor), Manuel, P. (Contributor), Rudić, S. (Contributor), J. Ramirez-Cuesta, A. (Contributor), Easun, T. L. (Contributor), Yang, S. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1lq7vd, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lq7vd&sid=DataCite
Dataset
CCDC 1479680: Experimental Crystal Structure Determination
Lu, Z. (Contributor), Godfrey, H. (Contributor), Da Silva, I. (Contributor), Cheng, Y. (Contributor), Savage, M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), Teat, S. J. (Contributor), Gagnon, K. J. (Contributor), Frogley, M. D. (Contributor), Manuel, P. (Contributor), Rudić, S. (Contributor), J. Ramirez-Cuesta, A. (Contributor), Easun, T. L. (Contributor), Yang, S. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 13 May 2016
DOI: 10.5517/ccdc.csd.cc1lnqml, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lnqml&sid=DataCite
Dataset

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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, 8, [14212]. https://doi.org/10.1038/ncomms14212

@article{d89d92848aae4606969d73dbdc6516cd,

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) {[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) {\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 Harry Godfrey and {Da Silva}, Ivan and Yongqiang Cheng and Mathew Savage and Floriana Tuna and Eric Mcinnes and Teat, {Simon J.} and Gagnon, {Kevin J.} and Frogley, {Mark D.} and Pascal Manuel and Svemir Rudi{\'c} and {J. Ramirez-Cuesta}, Anibal and Easun, {Timothy L.} and Sihai Yang and Martin Schroder",

year = "2017",

doi = "10.1038/ncomms14212",

language = "English",

volume = "8",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Springer Nature",

}

TY - JOUR

T1 - Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework

AU - Lu, Zhenzhong

AU - Godfrey, Harry

AU - Da Silva, Ivan

AU - Cheng, Yongqiang

AU - Savage, Mathew

AU - Tuna, Floriana

AU - Mcinnes, Eric

AU - Teat, Simon J.

AU - Gagnon, Kevin J.

AU - Frogley, Mark D.

AU - Manuel, Pascal

AU - Rudić, Svemir

AU - J. Ramirez-Cuesta, Anibal

AU - Easun, Timothy L.

AU - Yang, Sihai

AU - Schroder, Martin

PY - 2017

Y1 - 2017

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) {[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.

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) {[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.

U2 - 10.1038/ncomms14212

DO - 10.1038/ncomms14212

M3 - Article

VL - 8

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

M1 - 14212

ER -

Modulating Supramolecular Binding of Carbon Dioxide in a Redox-Active Porous Metal-Organic Framework

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Datasets

CCDC 1481146: Experimental Crystal Structure Determination

CCDC 1481144: Experimental Crystal Structure Determination

CCDC 1479680: Experimental Crystal Structure Determination

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