Inclusion chemistry of a thiazyl radical in zeolite-Y

Cowley, Hugh J.; Hayward, John; Pratt, Douglas; Rawson, Jeremy M.

doi:10.1039/c3dt52956h

Cited by 12 publications

(7 citation statements)

References 55 publications

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“…One study reports the inclusion of benzodithiazolyl and methylbenzodithiazolyl into MIL-53(Al), 19 while the other reports the inclusion of PhCNSSN • into Faujasite. 20 Notably, in the former complex the walls of the host cavity rotate to accommodate the guest, indicating a responsive relationship between the host and the guest.…”

Section: Inclusion Of the Dithiadiazolyl Radical Phcnssn • Into The Dmentioning

confidence: 99%

Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

et al. 2017

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Inclusion of the dithiadiazolyl radical PhCNSSN˙ into the dynamically porous metallocycle [Cu(L1)Cl], where L1 is the bidentate ligand 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, has been achieved by gas phase diffusion. Single crystal X-ray diffraction, powder X-ray diffraction, UV-visible spectroscopy, EPR and SQUID magnetometry studies confirm inclusion of the radical into this seemingly non-porous material, and illustrate the antiferromagnetic coupling between the paramagnetic host and guest species. The radical guest is readily released by heating or by the addition of solvent (CHCl).

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Section: Inclusion Of the Dithiadiazolyl Radical Phcnssn • Into The Dmentioning

confidence: 99%

Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

et al. 2017

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“…Small and structurally simple molecules that can be used as probes are also studied using this technique. − The electron spin resonance (ESR) spectroscopy is a powerful technique that can be used for the detection of organic radicals confined in the nanospaces of the material and nitroxide (NO) groups bonded to the material. The temperature dependence of the molecular dynamics of the confined radicals or NO moieties in the nanospace is studied to gain information on the structures, sizes, and shapes of the nanospaces present in porous materials, − crystals, polymers, liquid crystals, supercooled bulk water, biological membranes, , and proteins − using the ESR spin probe technique. The dynamics of the moieties bearing the unpaired electrons are influenced by the structures or shapes of the nanospaces.…”

Section: Introductionmentioning

confidence: 99%

“…The values of the g tensor and the hyperfine interaction ( A ) tensor of the unpaired electron are determined by analyzing the dynamics of the moieties bearing the unpaired electrons. The ESR spin probe techniques can be divided into two categories: (i) the spin-label method executed by functionalizing the NO groups in the material ,,,, and (ii) the method where the free radicals such as 4-substituted 2,2,6,6-tetramethyl-1-piperidinyloxyl (4- R -TEMPO; 1 : TEMPO ( R = H) and 2 : 4-hydroxy-TEMPO (TEMPOL; R = OH); Figure a) are physically adsorbed in the confined spaces. ,,− ,,,, …”

Section: Introductionmentioning

confidence: 99%

“…The ESR spin probe techniques can be divided into two categories: (i) the spin-label method executed by functionalizing the NO groups in the material 9,14,19,21,23 and (ii) the method where the free radicals such as 4-substituted 2,2,6,6-tetramethyl-1-piperidinyloxyl (4-R-TEMPO; 1: TEMPO (R = H) and 2: 4-hydroxy-TEMPO (TEMPOL; R = OH); Figure 1a) are physically adsorbed in the confined spaces. 7,8,[10][11][12][13]16,17,20,22 In the past decade, the ESR spin probe technique has been used to study the organic 1D nanochannels of 2,4,6-tris (4chlorophenoxy)-1,3,5-triazine and (o-phenylenedioxy)cyclotriphophazene crystals using 2-substituted nitronylnitroxide (2-X-NN, 3−5, Figure 1b). 24,25 Nitronylnitroxide (NN) radicals are common organic radicals.…”

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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“…In particular, the inclusion of organic radicals into organic 1D nanochannels could lead to the development of new organic magnets. Recently, several methods of constructing 1D organic radical molecular chains have been proposed using various organic and/or inorganic 1D porous materials as templates …”

Section: Introductionmentioning

confidence: 99%

ESR study of molecular orientation and dynamics of TEMPO derivatives in CLPOT 1D nanochannels

Kobayashi

Furuhashi

Nakagawa

et al. 2016

Magnetic Reson in Chemistry

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The molecular orientations and dynamics of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical derivatives with large substituent groups at the 4-position (4-X-TEMPO) in the organic one-dimensional nanochannels within the nanosized molecular template 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) were examined using ESR. The concentrations of guest radicals, including 4-methoxy-TEMPO (MeO-TEMPO) or 4-oxo-TEMPO (TEMPONE), in the CLPOT nanochannels in each inclusion compound (IC) were reduced by co-including 4-substituted-2,2,6,6-tetramethylpiperidine (4-R-TEMP) compounds at a ratio of 1 : 30-1 : 600. At higher temperatures, the guest radicals in each IC underwent anisotropic rotational diffusion in the CLPOT nanochannels. The rotational diffusion activation energy, Ea , associated with MeO-TEMPO or TEMPONE in the CLPOT nanochannels (6-7 kJ mol(-1) ), was independent of the size and type of substituent group and was similar to the Ea values obtained for TEMPO and 4- hydroxy-TEMPO (TEMPOL) in our previous study. However, in the case in which TEMP was used as a guest compound for dilution (spacer), the tilt of the rotational axis to the principal axis system of the g-tensor, and the rotational diffusion correlation time, τR , of each guest radical in the CLPOT nanochannels were different from the case with other 4-R-TEMP. These results indicate the possibility of controlling molecular orientation and dynamics of guest radicals in CLPOT ICs through the appropriate choice of spacer. Copyright © 2016 John Wiley & Sons, Ltd.

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Inclusion chemistry of a thiazyl radical in zeolite-Y

Cited by 12 publications

References 55 publications

Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

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

ESR study of molecular orientation and dynamics of TEMPO derivatives in CLPOT 1D nanochannels

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