Solid state NMR strategies for the structural characterization of new hybrid materials based on the intercalation of nitroxide radicals into CdPS3

Hemme, Wilhelm L.; Fujita, Wataru; Awaga, Kunio; Eckert, Hellmut

doi:10.1016/j.ssnmr.2011.03.006

Cited by 8 publications

(6 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This peak is still apparent at low loadings, where it is superimposed by the spectrum of the radical cation. Similar results have been obtained with various other radical species in Somasif , saponite and CdPS 3 …”

Section: Tuning Inter‐electronic Exchange Interactions In Radical Cosupporting

confidence: 88%

“…TEMPO‐ and nitronyl nitroxide derived radical cations can be intercalated into various inorganic layered host structures. Suitable host materials include saponite, hectorite, and cadmium phosphorus sulfide CdPS 3 . The spatial confinement within the interlayer space as well as the intermolecular interactions between the host lattice and the guest species can lead to greatly modified orientations of the spin carrying moieties and molecules compared to the situation in the molecular crystals, resulting in a range of interesting and unusual optical, magnetic, and catalytic properties.…”

Section: Tuning Inter‐electronic Exchange Interactions In Radical Comentioning

confidence: 99%

“…Large crystal structure databases have been generated by synthesizing many radical variants with different ring substituents, presenting a wide variety of magnetic properties, as the number of available stable free radicals is ever more expanding . Pursuing various crystal engineering approaches to modify the intermolecular interactions between (and thence the magnetic properties of) solid aminoxyl (and other) radical building blocks, these molecules have been integrated into various inorganic‐organic hybrid materials and/or nanocomposites, using concepts of coordination chemistry, self‐assembly on surfaces, or topotactic reactions . Designing particular physical properties of such hybrid systems requires an understanding and synthetic control of the local structural details originating from the various intermolecular interactions involved.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Eckert

2017

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Electron and nuclear spins are extremely sensitive probes of their local structural and dynamic surroundings. Their Zeeman energy levels are modified by different types of local magnetic and electric fields created by their structural environment, which influence their magnetic resonance condition. For this reason, electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopies have become extremely powerful tools of structural analysis, which are being widely used for the structural characterization of complex solids. Following a brief introduction into the basic theoretical foundations the most commonly used techniques and their application towards the structural characterization of paramagnetic solids based on aminoxyl radicals and their inorganic-organic nanocomposites will be described. Both ESR and NMR observables are useful for monitoring intermolecular interactions between unpaired electron spins, which are particularly important for the design of organically based ferromagnetic systems. ESR and NMR methods based on this effect can be used for monitoring the synthesis of polynitroxides and for evaluating the catalytic function of aminoxyl intercalation compounds. Finally, the sensitivity of ESR signals to motional dynamics can be exploited for characterizing molecule-surface interactions in nanocomposite systems. In the context of the latter work recently developed signal enhancement strategies are described, using polarization transfer from electron spins to nuclear spins for NMR spectroscopic detection.

show abstract

Section: Tuning Inter‐electronic Exchange Interactions In Radical Cosupporting

confidence: 88%

Section: Tuning Inter‐electronic Exchange Interactions In Radical Comentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Eckert

2017

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…This principle has been demonstrated for some layered crystalline host matrices such as the clay material saponite Na x Mg 3 Si 4−x Al x O 10 -(OH) 2 •nH 2 O and cadmium phosphorus sulfide CdPS 3 . [3][4][5][6][7] As previously discussed, such materials can be used as recyclable catalysts for the oxidation of alcohols. In the present study, we report the intercalation of three different types of radical cations, based on tetramethylpyridine N-oxide (TEMPO), a nitronyl nitroxide, and a viologen into a fluoromica clay material known under the trade name Somasif, Na 2x Mg 3.0−x -Si 4 O 10 (F y OH 1−y ) 2 (x = 0.33, y = 0.98).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of inorganic–organic hybrid materials based on the intercalation of stable organic radicals into a fluoromica clay

et al. 2013

Self Cite

View full text Add to dashboard Cite

Hybrid materials, in which stable organic radical cations are intercalated into layered inorganic host materials, can be successfully synthesized via an ion exchange reaction in a layered fluoromica clay, to yield recyclable heterogeneous catalysts for oxidation of various alcohols. We have conducted systematic synthetic and structural studies on the intercalation of the radical cations 4-(diethylmethylammonium)-2,2,6,6-tetramethylpiperidin-1-oxyl (DEMTEP), 1-[2-(4-amino-2,2,6,6-tetramethyl-1-piperidinyloxyl)-2-oxoethyl]-1'-methyl-4,4'-bipyridinium (VIOTEP), and 2-(3-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide (m-MPYNN) into a synthetic fluoromica clay named Somasif® ME 100, Na(2x)Mg(3.0-x)Si4O10(F(y)OH(1-y))2 (x = 0.33, y = 0.98). The guest-host interactions in these intercalation compounds have been characterized by X-ray powder diffraction and solid-state NMR of the constituent nuclei ((23)Na, (19)F, and (29)Si) of the Somasif structure. The intercalation process can be conveniently monitored using (23)Na MAS-NMR. Guest-guest interactions have been probed by magnetic susceptibility measurements as well as EPR and (1)H MAS NMR experiments. The (1)H MAS-NMR line widths and chemical shifts probe modifications in the electron spin density distributions and/or intermolecular interactions between the electron spins of the guest species. Despite these indications of weakly interacting spins, magnetic susceptibility measurements are consistent with the near-absence of cooperative magnetism. The VIOTEP and DEMTEP inclusion compounds demonstrate catalytic activity for the oxidation of benzyl alcohol, using NaOCl as a co-oxidant. Although the radical ion species is partially leached out under these conditions (ionic exchange with Na(+) in solution) the catalytic activity remains for up to 40 subsequent cycles. Fully leached materials can be regenerated by catalyst re-loading and this process can be conveniently monitored by X-band EPR spectroscopy.

show abstract

“…The study of single crystal has been an interesting field of research for more than two decades. This is because it gives an opportunity to understand the physical properties in low dimensions and to explore their vast potential for application [2][3][4][5][6]. Over the past two decades research on quantum sized single crystal particles has increased enormously due to their novel applications in electronic and photonic devices [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

A density functional theory study of Raman modes of cadmium hexathiohypodiphosphate (CdPS₃)

Shakoor

Hussain

Hassan

et al. 2015

Materials Science-Poland

View full text Add to dashboard Cite

Raman scattering investigations based on density functional theory (DFT) calculations were performed to explore the vibrational modes of a cadmium hexathiohypodiphosphate CdPS 3 single crystal. The calculations were performed to obtain the Raman spectra for the cadmium hexathiohypodiphosphate atoms to study the size dependence. Several vibrational modes indicating stretching and bending features related to Cd, S and P atoms were observed. Modifications of the frequency and intensity of different Raman modes with an increase in the number of atoms in CdPS 3 were discussed in detail. Hydrogen atoms were added in order to make the closed shell configuration and saturate the CdPS 3 as per the requisite for calculating the Raman spectra. This produced some additional modes of vibration related to hydrogen atoms. Band gap and formation energy were also calculated. The results generated are found to be in close agreement with the experimental values.

show abstract

Solid state NMR strategies for the structural characterization of new hybrid materials based on the intercalation of nitroxide radicals into CdPS3

Cited by 8 publications

References 16 publications

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Synthesis and characterization of inorganic–organic hybrid materials based on the intercalation of stable organic radicals into a fluoromica clay

A density functional theory study of Raman modes of cadmium hexathiohypodiphosphate (CdPS₃)

Contact Info

Product

Resources

About

Solid state NMR strategies for the structural characterization of new hybrid materials based on the intercalation of nitroxide radicals into CdPS3

Cited by 8 publications

References 16 publications

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic–Organic Nanocomposite Systems

Synthesis and characterization of inorganic–organic hybrid materials based on the intercalation of stable organic radicals into a fluoromica clay

A density functional theory study of Raman modes of cadmium hexathiohypodiphosphate (CdPS3)

Contact Info

Product

Resources

About

A density functional theory study of Raman modes of cadmium hexathiohypodiphosphate (CdPS₃)