Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 40, Pages 12351-12355Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201604730
Keywords
CO2 activation; coordination polymers; metal-organic frameworks; PCP pincer ligands; selective adsorption
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Funding
- NSF [DMR-1506694]
- Welch Foundation [F-1738]
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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 (PdCl)-Cl-II 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-N-3 modified version resists CO insertion under the same conditions.
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