title: Non-Interpenetrated Metal-Organic Frameworks Based on Copper(II) Paddlewheel and Oligoparaxylene-Isophthalate Linkers: Synthesis, Structure, and Gas Adsorption.
abstract: Two metal-organic framework materials, MFM-130 and MFM-131 (MFM = Manchester Framework Material), have been synthesized using two oligoparaxylene (OPX) tetracarboxylate linkers containing four and five aromatic rings, respectively. Both fof-type non-interpenetrated networks contain Kagomé lattice layers comprising [Cu2(COO)4] paddlewheel units and isophthalates, which are pillared by the OPX linkers. Desolvated MFM-130, MFM-130a, shows permanent porosity (BET surface area of 2173 m(2)/g, pore volume of 1.0 cm(3)/g), high H2 storage capacity at 77 K (5.3 wt% at 20 bar and 2.2 wt% at 1 bar), and a higher CH4 adsorption uptake (163 cm(3)(STP)/cm(3) (35 bar and 298 K)) compared with its structural analogue, NOTT-103. MFM-130a also shows impressive selective adsorption of C2H2, C2H4, and C2H6 over CH4 at room temperature, indicating its potential for separation of C2 hydrocarbons from CH4. The single-crystal structure of MFM-131 confirms that the methyl substituents of the paraxylene units block the windows in the Kagomé lattice layer of the framework, effectively inhibiting network interpenetration in MFM-131. This situation is to be contrasted with that of the doubly interpenetrated oligophenylene analogue, NOTT-104. Calculation of the mechanical properties of these two MOFs confirms and explains the instability of MFM-131 upon desolvation in contrast to the behavior of MFM-130. The incorporation of paraxylene units, therefore, provides an efficient method for preventing network interpenetration as well as accessing new functional materials with modified and selective sorption properties for gas substrates.
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.|School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, U.K.
authors.forename: Yong
authors.initials: Y
authors.lastname: Yan
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.|Department of Chemistry, University of Basel , St. Johanns-Ring 19, 4056 Basel, Switzerland.
authors.forename: Michal
authors.initials: M
authors.lastname: Juríček
authors.affiliation: Chimie ParisTech, PSL Research University , CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France.
authors.forename: François-Xavier
authors.initials: FX
authors.lastname: Coudert
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Nicolaas A
authors.initials: NA
authors.lastname: Vermeulen
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Sergio
authors.initials: S
authors.lastname: Grunder
authors.affiliation: Chemical and Environmental Sciences Laboratory, General Motors Corporation , Warren, Michigan 48090, United States.
authors.forename: Anne
authors.initials: A
authors.lastname: Dailly
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
authors.affiliation: School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, U.K.|School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, U.K.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder