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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(V III ) {[V III 2 (OH) 2 (L)], LH 4 =biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V IV ), [V IV 2 O 2 (L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V III ) shows the second highest CO 2 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 CO 2 , which binds in an end-on manner, =1.863(1) Å. In contrast, CO 2 -loaded MFM-300(V IV ) shows CO 2 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 CO 2 in the pores is directly influenced by these primary binding sites.

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1];  [1];  [1];  [4];  [4];  [5];  [2];  [2];  [3];  [6];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of Manchester (United Kingdom). School of Chemistry
  2. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division (CEMD)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  6. Cardiff Univ. (United Kingdom). School of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1356917
Alternate Identifier(s):
OSTI ID: 1379736
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; SC0001015
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, and Schröder, Martin. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. United States: N. p., 2017. Web. doi:10.1038/ncomms14212.
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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, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, & Schröder, Martin. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. United States. https://doi.org/10.1038/ncomms14212
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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, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, and Schröder, Martin. Mon . "Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework". United States. https://doi.org/10.1038/ncomms14212. https://www.osti.gov/servlets/purl/1356917.
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@article{osti_1356917,
title = {Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework},
author = {Lu, Zhenzhong and Godfrey, Harry G. W. and da Silva, Ivan and Cheng, Yongqiang and Savage, Mathew and Tuna, Floriana and McInnes, Eric J. L. and Teat, Simon J. and Gagnon, Kevin J. and Frogley, Mark D. and Manuel, Pascal and Rudić, Svemir and Ramirez-Cuesta, Anibal J. and Easun, Timothy L. and Yang, Sihai and Schröder, Martin},
abstractNote = {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)], LH 4 =biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V IV ), [V IV 2 O 2 (L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V III ) shows the second highest CO 2 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 CO 2 , which binds in an end-on manner, =1.863(1) Å. In contrast, CO 2 -loaded MFM-300(V IV ) shows CO 2 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 CO 2 in the pores is directly influenced by these primary binding sites.},
doi = {10.1038/ncomms14212},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Mon Feb 13 00:00:00 EST 2017},
month = {Mon Feb 13 00:00:00 EST 2017}
}
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https://doi.org/10.1038/ncomms14212
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Cited by: 63 works
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Figures / Tables:

Figure 1 Figure 1: Structures of MFM-300(V). Views of (a) MFM-300(VIII) and of (b) MFM-300(VIV). The pore size is ~6.7 6.7 Å for both MFM-300(VIII) and MFM-300(VIV) taking into consideration Van der Waals radii. The hydroxyl groups (green and red balls) in MFM-300(VIII) protrude into the channel, which change to O2- bridgemore » (shown as red ball) in MFM-300(VIV).« less
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