Gradual Release of Strongly-Bound Nitric Oxide from Fe2(NO)2(dobdc)

Published

February 24, 2015

Author(s)

Eric D. Bloch, Wendy L. Queen, Sachin Chavan, Paul S. Wheatley, Joseph M. Zadrozny, Russell E. Morris, Craig Brown, Carlo Lamberti, Silvia Bordiga, Jeffrey R. Long

Abstract

An iron-based metal-organic framework featuring coordinatively-unsaturated redox-active metal cation sites, Fe₂(dobdc) (dobdc^4- = 1,4-dioxido-2,5-benzenedicarboxylate), is shown to strongly bond nitric oxide at 298 K. Adsorption isotherms indicate an adsorption capacity greater than 16 mass %, corresponding to the adsorption of one NO molecule per iron center. Infrared, UV-vis, and Mossbauer spectroscopies, together with magnetic susceptibility data, confirm the strong binding is a result of electron transfer from the Fe_II site to form Fe^III-NO-adducts. Consistent with these results of, powder neutron diffraction experiments indicate that NO is bound to the iron centers of the framework with an Fe-NO separation of 1.77 (1) A and an Fe-N-O angle of 150.9 (5)°. The nitric oxide-containing material, Fe₂(NO)₂(dobdc), steadily releases bound NO under humid conditions over the course of more than 10 days, making it a much better candidate than other porous materials for certain biomedical applications.

Citation

Journal of the American Chemical Society

Volume

137

Pub Type

Journals

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Keywords

neutron diffraction, metal-organic framework, gas adsorption

Citation

Bloch, E. , Queen, W. , Chavan, S. , Wheatley, P. , Zadrozny, J. , Morris, R. , Brown, C. , Lamberti, C. , Bordiga, S. and Long, J. (2015), Gradual Release of Strongly-Bound Nitric Oxide from Fe₂(NO)₂(dobdc), Journal of the American Chemical Society, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=917809 (Accessed March 13, 2025)