CO Binding at a Four-Coordinate Cobaltous Porphyrin Site in a Metal-Organic Framework: Structural, EPR, and Gas Adsorption Analysis

Audrey T. Gallagher, Christos D. Malliakas, T. David Harris*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

The variable-temperature CO binding at a four-coordinate cobaltous porphyrin complex within a metal-organic framework is investigated using a combined array of infrared, X-ray diffraction, EPR, and CO adsorption analysis. Single-crystal X-ray diffraction experiments provide the first crystallographically characterized example of a noniron first-row transition metal porphyrin carbonyl adduct. Variable-temperature electron paramagnetic resonance spectroscopy supports the structural observation and reveals conversion of the dicarbonyl complex to a monocarbonyl species as temperature is increased. Finally, CO adsorption analysis data enable quantification of the Co-CO interaction, providing a binding enthalpy of hads = -29(2) kJ/mol. This value is nearly twice that observed for O2 binding in the same compound and is attributed to a stronger σ interaction for Co and CO vs O2. These results demonstrate the ability of MOFs to enable a thorough investigation of CO binding in metalloporphyrins.

Original languageEnglish (US)
Pages (from-to)4654-4661
Number of pages8
JournalInorganic chemistry
Volume56
Issue number8
DOIs
StatePublished - Apr 17 2017

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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