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Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks

Nitric oxide (NO) is an important signaling molecule in biological systems, and as such, the ability of porous materials to reversibly adsorb NO is of interest for potential medical applications. Although certain metal–organic frameworks are known to bind NO reversibly at coordinatively unsaturated...

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Autores principales: Oktawiec, Julia, Jiang, Henry Z. H., Turkiewicz, Ari B., Long, Jeffrey R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8580060/
https://www.ncbi.nlm.nih.gov/pubmed/34881011
http://dx.doi.org/10.1039/d1sc03994f
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author Oktawiec, Julia
Jiang, Henry Z. H.
Turkiewicz, Ari B.
Long, Jeffrey R.
author_facet Oktawiec, Julia
Jiang, Henry Z. H.
Turkiewicz, Ari B.
Long, Jeffrey R.
author_sort Oktawiec, Julia
collection PubMed
description Nitric oxide (NO) is an important signaling molecule in biological systems, and as such, the ability of porous materials to reversibly adsorb NO is of interest for potential medical applications. Although certain metal–organic frameworks are known to bind NO reversibly at coordinatively unsaturated metal sites, the influence of the metal coordination environment on NO adsorption has not been studied in detail. Here, we examine NO adsorption in the frameworks Co(2)Cl(2)(bbta) (H(2)bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) and Co(2)(OH)(2)(bbta) using gas adsorption, infrared spectroscopy, powder X-ray diffraction, and magnetometry. At room temperature, NO adsorbs reversibly in Co(2)Cl(2)(bbta) without electron transfer, with low temperature data supporting spin-crossover of the NO-bound cobalt(ii) centers of the material. In contrast, adsorption of low pressures of NO in Co(2)(OH)(2)(bbta) is accompanied by charge transfer from the cobalt(ii) centers to form a cobalt(iii)–NO(−) adduct, as supported by diffraction and infrared spectroscopy data. At higher pressures of NO, characterization data indicate additional uptake of the gas and disproportionation of the bound NO to form a cobalt(iii)–nitro (NO(2)(−)) species and N(2)O gas, a transformation that appears to be facilitated by secondary sphere hydrogen bonding interactions between the bound NO(2)(−) and framework hydroxo groups. These results provide a rare example of reductive NO binding in a cobalt-based metal–organic framework, and they demonstrate that NO uptake can be tuned by changing the primary and secondary coordination environment of the framework metal centers.
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spelling pubmed-85800602021-12-07 Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks Oktawiec, Julia Jiang, Henry Z. H. Turkiewicz, Ari B. Long, Jeffrey R. Chem Sci Chemistry Nitric oxide (NO) is an important signaling molecule in biological systems, and as such, the ability of porous materials to reversibly adsorb NO is of interest for potential medical applications. Although certain metal–organic frameworks are known to bind NO reversibly at coordinatively unsaturated metal sites, the influence of the metal coordination environment on NO adsorption has not been studied in detail. Here, we examine NO adsorption in the frameworks Co(2)Cl(2)(bbta) (H(2)bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) and Co(2)(OH)(2)(bbta) using gas adsorption, infrared spectroscopy, powder X-ray diffraction, and magnetometry. At room temperature, NO adsorbs reversibly in Co(2)Cl(2)(bbta) without electron transfer, with low temperature data supporting spin-crossover of the NO-bound cobalt(ii) centers of the material. In contrast, adsorption of low pressures of NO in Co(2)(OH)(2)(bbta) is accompanied by charge transfer from the cobalt(ii) centers to form a cobalt(iii)–NO(−) adduct, as supported by diffraction and infrared spectroscopy data. At higher pressures of NO, characterization data indicate additional uptake of the gas and disproportionation of the bound NO to form a cobalt(iii)–nitro (NO(2)(−)) species and N(2)O gas, a transformation that appears to be facilitated by secondary sphere hydrogen bonding interactions between the bound NO(2)(−) and framework hydroxo groups. These results provide a rare example of reductive NO binding in a cobalt-based metal–organic framework, and they demonstrate that NO uptake can be tuned by changing the primary and secondary coordination environment of the framework metal centers. The Royal Society of Chemistry 2021-10-19 /pmc/articles/PMC8580060/ /pubmed/34881011 http://dx.doi.org/10.1039/d1sc03994f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Oktawiec, Julia
Jiang, Henry Z. H.
Turkiewicz, Ari B.
Long, Jeffrey R.
Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title_full Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title_fullStr Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title_full_unstemmed Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title_short Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
title_sort influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8580060/
https://www.ncbi.nlm.nih.gov/pubmed/34881011
http://dx.doi.org/10.1039/d1sc03994f
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