Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (
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 PdIICl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with CoIIions 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−CH3activated material undergoes rapid insertion of CO2gas to give Pd−OC(O)CH3at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2over CO, a Pd−N3modified version resists CO insertion under the same conditions.
more » « less- NSF-PAR ID:
- 10037873
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 128
- Issue:
- 40
- ISSN:
- 0044-8249
- Format(s):
- Medium: X Size: p. 12539-12543
- Size(s):
- ["p. 12539-12543"]
- Sponsoring Org:
- National Science Foundation
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