Theoretical Insights into the Tuning of Metal Binding Sites of Paddlewheels in rht-Metal-Organic Frameworks

Tony Pham, Katherine A. Forrest, Wen-Yang Gao, Shengqian Ma, Brian Space

Research output: Contribution to journalArticlepeer-review

14 Scopus citations


Theoretical investigations of CO2 sorption are performed in four members of the highly tunable rht-metal-organic framework (MOF) platform. rht-MOFs contain two Cu2+ ions that comprise the metal paddlewheels and both are in chemically distinct environments. Indeed, one type of Cu2+ ion faces toward the center of the linker whereas the other type faces away from the center of the linker. Electronic structure calculations on the series of rht-MOFs demonstrate that one of the Cu2+ ions has a consistently higher charge magnitude relative to the other. As a consequence, the Cu2+ ion with the higher partial positive charge acts as the favored sorbate binding site at initial loading as revealed by grand canonical Monte Carlo (GCMC) simulations that include many-body polarization. It was found that the charge distribution about the copper paddlewheels is dependent on the type of functional groups present on the linker. This study demonstrates how the binding site about the metal paddlewheels in the rht-MOF platform can be controlled by changing the functionality on the organic ligand.
Original languageEnglish (US)
Pages (from-to)3170-3179
Number of pages10
Issue number15
StatePublished - 2015
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2021-11-04
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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry


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