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

Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here in this paper 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 2O 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, OH∙∙∙ =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 CO$$_2$$···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. Lastly, the macroscopic packing of CO 2 in the pores is directly influenced by these primary binding sites.
 [1] ;  [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [1] ;  [1] ;  [1] ;  [4] ;  [4] ;  [5] ;  [2] ;  [2] ;  [3] ;  [6] ;  [1] ;  [1]
  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:
Grant/Contract Number:
AC05-00OR22725; AC02-05CH11231; SC0001015
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1379736