title: A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State.
abstract: A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction. The Pd-Cl groups inside the pores are accessible to post-synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd-CH3 activated material undergoes rapid insertion of CO2 gas to give Pd-OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd-N3 modified version resists CO insertion under the same conditions.
authors.affiliation: Department of Chemistry, The University of Texas at Austin, NHB 6.336, 100 E. 24th St. Stop A1590, Austin, TX, 78712, USA.
authors.forename: Junpeng
authors.initials: J
authors.lastname: He
authors.affiliation: Department of Chemistry, The University of Texas at Austin, NHB 6.336, 100 E. 24th St. Stop A1590, Austin, TX, 78712, USA.
authors.forename: Nolan W
authors.initials: NW
authors.lastname: Waggoner
authors.affiliation: Department of Chemistry, The University of Texas at Austin, NHB 6.336, 100 E. 24th St. Stop A1590, Austin, TX, 78712, USA.
authors.forename: Samuel G
authors.initials: SG
authors.lastname: Dunning
authors.affiliation: Department of Chemistry, University of Liverpool, Crown St., Liverpool, L69 7ZD, UK.
authors.forename: Alexander
authors.initials: A
authors.lastname: Steiner
authors.affiliation: Department of Chemistry, The University of Texas at Austin, NHB 6.336, 100 E. 24th St. Stop A1590, Austin, TX, 78712, USA.
authors.forename: Vincent M
authors.initials: VM
authors.lastname: Lynch
authors.affiliation: Department of Chemistry, The University of Texas at Austin, NHB 6.336, 100 E. 24th St. Stop A1590, Austin, TX, 78712, USA. smh@cm.utexas.edu.
authors.forename: Simon M
authors.initials: SM
authors.lastname: Humphrey
keywords: CO2 activation; PCP pincer ligands; coordination polymers; metal-organic frameworks; selective adsorption