Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex

An ESR spin probe technique with non-TEMPO radicals, such as nitronyl nitroxide (NN), benzonitronyl nitroxide (BzNN), and iminonitroxide (IN) radicals, was used for a porous metal-organic framework (MOF), [(ZnI2)3(TPT)2] (ZnTPT; TPT = tris(4-pyridyl)-1,3,5-triazine), at room temperature. The princip...

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Main Authors: Hirokazu Kobayashi, Kento Akiniwa, Fumiyasu Iwahori, Hidehiko Honda, Masato Yamamoto
Format: Article
Language:English
Published: Wiley 2024-01-01
Series:Concepts in Magnetic Resonance: Part A, Bridging Education and Research
Online Access:http://dx.doi.org/10.1155/2024/1969686
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author Hirokazu Kobayashi
Kento Akiniwa
Fumiyasu Iwahori
Hidehiko Honda
Masato Yamamoto
author_facet Hirokazu Kobayashi
Kento Akiniwa
Fumiyasu Iwahori
Hidehiko Honda
Masato Yamamoto
author_sort Hirokazu Kobayashi
collection DOAJ
description An ESR spin probe technique with non-TEMPO radicals, such as nitronyl nitroxide (NN), benzonitronyl nitroxide (BzNN), and iminonitroxide (IN) radicals, was used for a porous metal-organic framework (MOF), [(ZnI2)3(TPT)2] (ZnTPT; TPT = tris(4-pyridyl)-1,3,5-triazine), at room temperature. The principal values of g and hyperfine coupling (A) tensors estimated from spectral reproduction were different from those for organic matrices for some of these radicals. These results indicate that host-guest interactions occur between the ZnTPT matrix and guest radicals. Thus, when using NN, BzNN, and IN radicals as spin probes for a porous MOF, the interaction between the metal atoms or organic ligands in host materials and guest radicals should be considered. The experimental ESR spectra for the derivatives of NN or BzNN radicals were reproduced only by the rigid-limit component in the ESR time scale. However, those for the derivatives of IN radicals were approximately reproduced only by rotational diffusion around the z-axis perpendicular to the plane in the IN group. Interestingly, this reproduction was not around the y-axis of the principal axes of the g tensors, parallel to the molecular long axis, as previously observed in a few organic matrices. The IN radicals dispersed in the ZnTPT matrix are expected to be accommodated in cylindrical or pseudocylindrical nanospaces sandwiched by the pyridyl or triazine rings of TPT in ZnTPT. These findings show that the ESR spin probe technique using non-TEMPO radicals can be used to investigate the chemical and biological structures of nanosized materials.
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spelling doaj-art-a815fa6e20474da99d01db460d029c702025-01-03T01:30:48ZengWileyConcepts in Magnetic Resonance: Part A, Bridging Education and Research1552-50232024-01-01202410.1155/2024/1969686Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn ComplexHirokazu Kobayashi0Kento Akiniwa1Fumiyasu Iwahori2Hidehiko Honda3Masato Yamamoto4Faculty of Arts and Sciences at FujiyoshidaGraduate School of Integrated Basic SciencesDepartment of ChemistryFaculty of Arts and Sciences at FujiyoshidaFaculty of Arts and Sciences at FujiyoshidaAn ESR spin probe technique with non-TEMPO radicals, such as nitronyl nitroxide (NN), benzonitronyl nitroxide (BzNN), and iminonitroxide (IN) radicals, was used for a porous metal-organic framework (MOF), [(ZnI2)3(TPT)2] (ZnTPT; TPT = tris(4-pyridyl)-1,3,5-triazine), at room temperature. The principal values of g and hyperfine coupling (A) tensors estimated from spectral reproduction were different from those for organic matrices for some of these radicals. These results indicate that host-guest interactions occur between the ZnTPT matrix and guest radicals. Thus, when using NN, BzNN, and IN radicals as spin probes for a porous MOF, the interaction between the metal atoms or organic ligands in host materials and guest radicals should be considered. The experimental ESR spectra for the derivatives of NN or BzNN radicals were reproduced only by the rigid-limit component in the ESR time scale. However, those for the derivatives of IN radicals were approximately reproduced only by rotational diffusion around the z-axis perpendicular to the plane in the IN group. Interestingly, this reproduction was not around the y-axis of the principal axes of the g tensors, parallel to the molecular long axis, as previously observed in a few organic matrices. The IN radicals dispersed in the ZnTPT matrix are expected to be accommodated in cylindrical or pseudocylindrical nanospaces sandwiched by the pyridyl or triazine rings of TPT in ZnTPT. These findings show that the ESR spin probe technique using non-TEMPO radicals can be used to investigate the chemical and biological structures of nanosized materials.http://dx.doi.org/10.1155/2024/1969686
spellingShingle Hirokazu Kobayashi
Kento Akiniwa
Fumiyasu Iwahori
Hidehiko Honda
Masato Yamamoto
Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
Concepts in Magnetic Resonance: Part A, Bridging Education and Research
title Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
title_full Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
title_fullStr Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
title_full_unstemmed Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
title_short Electron Spin Resonance Spin Probe Technique for Investigating Non-TEMPO Radicals Dispersed in Nanospaces of a Crystalline Zn Complex
title_sort electron spin resonance spin probe technique for investigating non tempo radicals dispersed in nanospaces of a crystalline zn complex
url http://dx.doi.org/10.1155/2024/1969686
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