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 CO2uptake 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 CO2bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ···c.g.phenylinteraction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2in the pores is directly influenced by these primary binding sites.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Zhenzhong
authors.initials: Z
authors.lastname: Lu
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Harry G W
authors.initials: HG
authors.lastname: Godfrey
authors.affiliation: ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Ivan
authors.identifier: 0000-0002-4472-9675
authors.initials: I
authors.lastname: da Silva
authors.affiliation: The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Yongqiang
authors.initials: Y
authors.lastname: Cheng
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Mathew
authors.identifier: 0000-0002-9078-1845
authors.initials: M
authors.lastname: Savage
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes
authors.affiliation: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Teat
authors.affiliation: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Kevin J
authors.initials: KJ
authors.lastname: Gagnon
authors.affiliation: Diamond Light Source, Harwell Science Campus, Oxfordshire OX11 0DE, UK.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Frogley
authors.affiliation: ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Pascal
authors.initials: P
authors.lastname: Manuel
authors.affiliation: ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Svemir
authors.initials: S
authors.lastname: Rudić
authors.affiliation: The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Anibal J
authors.initials: AJ
authors.lastname: Ramirez-Cuesta
authors.affiliation: School of Chemistry, Cardiff University, Cardiff CF10 3XQ, UK.
authors.forename: Timothy L
authors.initials: TL
authors.lastname: Easun
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Sihai
authors.initials: S
authors.lastname: Yang
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder