Long-Lived Photoinduced Charge Separation in a Trinuclear Iron-μ3-oxo-based Metal-Organic Framework

Lauren Hanna, Pavel Kucheryavy, Cunming Liu, Xiaoyi Zhang, Jenny V. Lockard

Research output: Contribution to journalArticlepeer-review

33 Scopus citations


The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge-separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. We investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), composed of Fe33-oxo clusters and trimesic acid linkers, using Fe K-edge X-ray transient absorption (XTA) spectroscopy to unambiguously determine its ligand-to-metal charge-transfer character. Spectra measured at time delays up to 3.6 μs confirm the long-lived nature of the charge-separated excited state. Several trinuclear iron μ3-oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady-state X-ray absorption spectroscopy and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements, so both its fabrication and particle size analysis are presented as well.

Original languageEnglish (US)
Pages (from-to)13570-13576
Number of pages7
JournalJournal of Physical Chemistry C
Issue number25
StatePublished - Jun 29 2017

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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