Gradual release of strongly bound nitric oxide from Fe2(NO)2(dobdc)

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

doi:10.1021/ja5132243

Gradual release of strongly bound nitric oxide from Fe₂(NO)₂(dobdc)

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

Research output: Contribution to journal › Article › peer-review

Abstract

An iron(II)-based metal–organic framework featuring coordinatively unsaturated redox-active metal cation sites, Fe₂(dobdc) (dobdc^4– = 2,5-dioxido-1,4-benzenedicarboxylate), is shown to strongly bind nitric oxide at 298 K. Adsorption isotherms indicate an adsorption capacity greater than 16 wt %, corresponding to the adsorption of one NO molecule per iron center. Infrared, UV–vis, and Mössbauer spectroscopies, together with magnetic susceptibility data, confirm the strong binding is a result of electron transfer from the Fe^II sites to form Fe^III–NO– adducts. Consistent with these results, 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) Å 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, suggesting it, and potential future iron(II)-based metal–organic frameworks, are good candidates for certain biomedical applications.

Original language	English
Pages (from-to)	3466-3469
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	10
Early online date	24 Feb 2015
DOIs	https://doi.org/10.1021/ja5132243
Publication status	Published - 18 Mar 2015

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Copyright © 2015 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see: http://dx.doi.org/10.1021/ja5132243
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@article{89062c704d6d42c4bf7cfa1f1c419664,

title = "Gradual release of strongly bound nitric oxide from Fe2(NO)2(dobdc)",

abstract = "An iron(II)-based metal–organic framework featuring coordinatively unsaturated redox-active metal cation sites, Fe2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), is shown to strongly bind nitric oxide at 298 K. Adsorption isotherms indicate an adsorption capacity greater than 16 wt \%, corresponding to the adsorption of one NO molecule per iron center. Infrared, UV–vis, and M{\"o}ssbauer spectroscopies, together with magnetic susceptibility data, confirm the strong binding is a result of electron transfer from the FeII sites to form FeIII–NO– adducts. Consistent with these results, 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) {\AA} 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, suggesting it, and potential future iron(II)-based metal–organic frameworks, are good candidates for certain biomedical applications.",

author = "Bloch, \{Eric D.\} and Queen, \{Wendy L.\} and Sachin Chavan and Wheatley, \{Paul Stewart\} and Zadrozny, \{Joseph M.\} and Morris, \{Russell Edward\} and Brown, \{Craig M.\} and Carlo Lamberti and Silvia Bordiga and Long, \{Jeffrey R.\}",

note = "This research was supported through the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0001015. We thank Arkema and Gerald K. Branch for fellowship support of E.D.B. and Ateneo Project 2011 ORTO11RRT5 for financial support of S.B., C.L., and S.C. C.L. acknowledges the Mega-grant of the Russian Federation Government number 14.Y26.31.0001 for support.",

year = "2015",

month = mar,

day = "18",

doi = "10.1021/ja5132243",

language = "English",

volume = "137",

pages = "3466--3469",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Gradual release of strongly bound nitric oxide from Fe2(NO)2(dobdc)

AU - Bloch, Eric D.

AU - Queen , Wendy L.

AU - Chavan, Sachin

AU - Wheatley, Paul Stewart

AU - Zadrozny, Joseph M.

AU - Morris, Russell Edward

AU - Brown , Craig M.

AU - Lamberti, Carlo

AU - Bordiga, Silvia

AU - Long , Jeffrey R.

N1 - This research was supported through the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0001015. We thank Arkema and Gerald K. Branch for fellowship support of E.D.B. and Ateneo Project 2011 ORTO11RRT5 for financial support of S.B., C.L., and S.C. C.L. acknowledges the Mega-grant of the Russian Federation Government number 14.Y26.31.0001 for support.

PY - 2015/3/18

Y1 - 2015/3/18

N2 - An iron(II)-based metal–organic framework featuring coordinatively unsaturated redox-active metal cation sites, Fe2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), is shown to strongly bind nitric oxide at 298 K. Adsorption isotherms indicate an adsorption capacity greater than 16 wt %, corresponding to the adsorption of one NO molecule per iron center. Infrared, UV–vis, and Mössbauer spectroscopies, together with magnetic susceptibility data, confirm the strong binding is a result of electron transfer from the FeII sites to form FeIII–NO– adducts. Consistent with these results, 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) Å 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, suggesting it, and potential future iron(II)-based metal–organic frameworks, are good candidates for certain biomedical applications.

AB - An iron(II)-based metal–organic framework featuring coordinatively unsaturated redox-active metal cation sites, Fe2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), is shown to strongly bind nitric oxide at 298 K. Adsorption isotherms indicate an adsorption capacity greater than 16 wt %, corresponding to the adsorption of one NO molecule per iron center. Infrared, UV–vis, and Mössbauer spectroscopies, together with magnetic susceptibility data, confirm the strong binding is a result of electron transfer from the FeII sites to form FeIII–NO– adducts. Consistent with these results, 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) Å 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, suggesting it, and potential future iron(II)-based metal–organic frameworks, are good candidates for certain biomedical applications.

UR - http://pubs.acs.org/doi/suppl/10.1021/ja5132243

UR - https://www.scopus.com/pages/publications/84925277989

U2 - 10.1021/ja5132243

DO - 10.1021/ja5132243

M3 - Article

AN - SCOPUS:84925277989

SN - 0002-7863

VL - 137

SP - 3466

EP - 3469

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 10

ER -

Gradual release of strongly bound nitric oxide from Fe₂(NO)₂(dobdc)

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Russell Morris, FRS FRSE FRSC FLSW

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Gradual release of strongly bound nitric oxide from Fe2(NO)2(dobdc)

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Russell Morris, FRS FRSE FRSC FLSW

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Gradual release of strongly bound nitric oxide from Fe₂(NO)₂(dobdc)