Modeling PCN-61 and PCN-66: Isostructural rht -Metal–Organic Frameworks with Distinct CO 2 Sorption Mechanisms

Tony Pham, Katherine A. Forrest, Kyle McDonald, Brian Space

Research output: Contribution to journalArticlepeer-review

23 Scopus citations


© 2014 American Chemical Society. Simulations of CO2 sorption were performed in two members of the highly tunable rht-metal-organic framework (MOF) platform: PCN-61 and PCN-66. These MOFs differ only in the triisophthalate ligand used to synthesize the respective MOFs. In PCN-61, the center of the ligand contains a benzene ring; this ring is substituted with a triphenylamine group in PCN-66. There are two chemically distinct Cu2+ ions that comprise the copper paddlewheels, [Cu2(O2CR)4], in all rht-MOFs. One type of Cu2+ ion, denoted Cu1, projects into the truncated tetrahedral (T-Td) and truncated octahedral (T-Oh) cages, while the other Cu2+ ion, denoted Cu2, projects into the cuboctahedral (cub-Oh) cages. Electronic structure calculations revealed that, in PCN-61, the Cu2 ions have a significantly higher partial positive charge than the Cu1 ions, whereas the opposite was observed in PCN-66. The simulations revealed that the CO2 molecules sorb initially onto the Cu2+ ions that have the higher partial positive charge, i.e., the Cu2 ions in PCN-61 and the Cu1 ions in PCN-66. This was demonstrated by examining the radial distribution function, g(r), about both Cu2+ ions and the modeled structure at low loading for both MOFs. This study provided insights into how differences in the charge distributions about the copper paddlewheels between two isostructural MOFs, arising from the choice of functionality on the ligand, can lead to different CO2 binding sites at low loading and suggests a more general conceptual framework for controlling sorption through the tuning of MOF electronics.
Original languageEnglish (US)
Pages (from-to)5599-5607
Number of pages9
JournalCrystal Growth & Design
Issue number11
StatePublished - Oct 9 2014
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): FIC/2010/06
Acknowledgements: This work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under an XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors would like to acknowledge the use of the services provided by Research Computing at the University of South Florida. K.M. acknowledges the NSF Graduate Research Fellowship Program (GRFP) and the Rackham Merit Fellowship (RMF).
This publication acknowledges KAUST support, but has no KAUST affiliated authors.


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