Shape‐Defined and Shape‐Shifting Paramagnetic Organic Nano/Microstructures Derived From a Doublet State Nitronyl Nitroxide Radical

Hui, Pramiti; Chandrasekar, Rajadurai

doi:10.1002/cplu.201200143

Cited by 3 publications

(3 citation statements)

References 45 publications

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“…These results revealed that the ESR spin probe technique could be used to study samples using non-TEMPO derivatives to study the chemical and biological structures of nanosized materials (such as nanosized cavities, polymers, membranes, and dental materials). The existence of the nanosized spaces containing the imino or nitronyl nitroxide groups has been reported in recent years. ,, The results reported herein can be used to develop such novel systems. The radicals used may be introduced inside the preformed pores in the polymer samples by exposing in a sealed test tube to conditions of reduced pressure or penetrating in the radical solution.…”

Section: Discussionmentioning

confidence: 62%

“…The existence of the nanosized spaces containing the imino or nitronyl nitroxide groups has been reported in recent years. 34,65,66 The results reported herein can be used to develop such novel systems. The radicals used may be introduced inside the preformed pores in the polymer samples by exposing a sealed test tube to conditions of reduced pressure or penetrating in the radical solution.…”

Section: Discussionmentioning

confidence: 90%

“…Several radicals belonging to this group of radicals behave as organic magnets at low temperatures. , Various NN radicals are present in the ligands in magnetic metal complexes − and metal–organic frameworks (MOFs) . Studies on the 2- X -NN radical present in frozen organic matrices, cement, and porous organic films have been rarely conducted using the ESR spectroscopy. − …”

Section: Introductionmentioning

confidence: 99%

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Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique

et al. 2021

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The electron spin resonance (ESR) spectroscopy technique was used to study various organic radicals, such as 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), 4-hydroxy-TEMPO (TEMPOL), 2-X-nitronylnitroxide (2-X-NN, X = Ph, NO 2 Ph, or cyclohexyl), 4-Ybenzonitronylnitroxide (4-Y-PhBzNN, Y = Ph or NO 2 Ph), and 2-Z-iminonitroxide (2-Z-IN, Z = Ph or NO 2 Ph) dispersed in a polymethylmethacrylate (PMMA) matrix. The experiments were conducted at room temperature. The complex nature of the recorded ESR spectra could be attributed to the superposition of the rotational diffusion component of TEMPO (or TEMPOL) in the nanospace of the PMMA matrix with the rigid-limit component. A single component of the rigid-limit was observed for 2-X-NN and 4-Y-PhBzNN radicals dispersed in the PMMA matrix. The isotropic components of g and hyperfine (A) tensor, estimated by analyzing the solution spectra, were used to determine the g and A components of 4-Y-PhBzNN. Only the rotational diffusion component was observed for the 2-Z-IN radical. These results demonstrated that the PMMA matrix contains cylindrical nanospaces. Various radicals other than TEMPO derivatives could be used in the ESR spin probe technique as probe molecules for determining the structures, sizes, and shapes of the nanospaces.

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Section: Discussionmentioning

confidence: 62%

Section: Discussionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique

et al. 2021

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Tuning the Magnetic Properties of Columnar Benzo[e][1,2,4]triazin‐4‐yls with the Molecular Shape

et al. 2019

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A homologous series of disc-like 1,3,6-trisubstituted benzo [e] [1,2,4]triazin-4-yls 1[n] was synthesized and their structural, thermal, optical, magnetic, and electric properties were investigated. The results demonstrate that all members of the series display a Col h phase with clearing temperatures depending on the length of the alkoxy chains at the N(1) position, hence the shape of the disc. Powder XRD and magnetic data indicate a gradual change in the column diameter and magnetic behavior in the series in transition from half-disc in 1[0] (antiferromagnetic interactions) to full-disc geometry in the 1[12] homologue (ferromagnetic interactions with J/k B = + 7.5 K). Studies of binary systems revealed that a 1 : 1 mixture of 1[0] and 1[12] exhibits modest stabilization of the Col h phase with an expanded range, and magnetic behavior typical for 1[0] in the rigid phase obtained from the melt. Electric measurements demonstrated hole mobility of~10 À 3 cm 2 V À 1 s À 1 and dark conductivity of~10 À 11 Scm À 1 in the mixture and individual compounds. The latter is enhanced up to 4 times by simultaneous illumination with UV light.[a] Dr.

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

Kobayashi,

Akiniwa,

Iwahori

et al. 2024

Concepts in Magnetic Resonance Part A

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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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Shape‐Defined and Shape‐Shifting Paramagnetic Organic Nano/Microstructures Derived From a Doublet State Nitronyl Nitroxide Radical

Cited by 3 publications

References 45 publications

Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique

Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique

Tuning the Magnetic Properties of Columnar Benzo[e][1,2,4]triazin‐4‐yls with the Molecular Shape

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

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