A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State

He, J, Waggoner, NW, Dunning, SG, Steiner, A ORCID: 0000-0002-4315-6123, Lynch, VM and Humphrey, SM (2016) A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State Angewandte Chemie (International ed. in English), 55 (40). pp. 12351-12355. ISSN 1433-7851, 1521-3773

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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.

Item Type:	Article
Uncontrolled Keywords:	PCP-pincer, coordination polymer, Metal-Organic Framework, CO2 activation, selective adsorption
Depositing User:	Symplectic Admin
Date Deposited:	19 Aug 2016 11:51
Last Modified:	01 Mar 2026 03:14
DOI:	10.1002/anie.201604730
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3002993
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