Electron spin resonance study of CH3CNSSN˙, C6H5CNSSN˙, and SNSSN˙+free radicals

Fairhurst, Shirley A.; Johnson, Karen M.; Sutcliffe, L. H.; Preston, K. F.; Banister, Arthur J.; Hauptman, Z.; Passmore, Jack

doi:10.1039/dt9860001465

Cited by 99 publications

(85 citation statements)

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“…3, 4) are those of the selenium-containing radical;. Both powder spectra bear a close resemblance to the known spectrum of S3N2+ (7,8) with three distinct g-features, only one of which displayed a resolved hyperfine manifold due to interaction with two equivalent 14N (I = 1) nuclei (Figs. 3,4).…”

Section: Resultsmentioning

confidence: 78%

“…An additional weak feature of the solution spectra (Fig. 2) consisted of a 1:2:3:2: 1 quintet with isotropic g , 14N hyperfine coupling, and linewidth parameters characteristic of the radical S3N2+ (7,8). This radical was clearly present in traces only and its spectral intensity varied from sample to sample.…”

Section: Resultsmentioning

confidence: 99%

“…1 and an 2A2 ground state (7)(8)(9). Experiment has shown that the two equivalent sulphur nuclei in that species make important 3p, contributions to the SOMO, whereas the unique sulphur nucleus makes only a small, indirect contribution through spin polarization (7)(8)(9).…”

Section: Discussionmentioning

confidence: 99%

“…spectroscopic studies (6)(7)(8)(9) have shown that this species is a As an unsurpassed probe of unpaired electron spin density, planar n-radical having the structure shown in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

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A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)

Awere¹,

Passmore²,

Preston³

et al. 1988

Can. J. Chem.

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Electron spin resonance spectra observed in dilute solutions of the hexafluoroarsenate salts of selenothiadiazolylium cations in I --polar solvents are ascribed to the parent cation radicals SeNSeSeN', SNSeSeN', ~N S~S A ' , and SNSSN+ . The g-and nitrogen hyperfine tensors for the three selenium-containing species are entirely in line with the planar w-radical description deduced in earlier studies of trithiadiazolylium. Substantial increases in the g-shifts on substitution of sulphur by selenium result in broadening of the solution spectra and concomitant loss of nitrogen hyperfine structure. From measurements made in solid SOz, the following principal tensor components were deduced for the new, Se-containing radicals: -N+: g = (1.9930, 2.0108, 2.1379), aN(2) = (7.4, -0, -0) gauss, ase(2) = (180, 70, 43) gauss; -N+: g = (1.9941, 2.0108, 2.1355), aN(2) = (6.9, -0, =0) gauss, ase (2) [Traduit par la revue]

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Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

“…spectroscopic studies (6)(7)(8)(9) have shown that this species is a As an unsurpassed probe of unpaired electron spin density, planar n-radical having the structure shown in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

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A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)

Awere¹,

Passmore²,

Preston³

et al. 1988

Can. J. Chem.

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“…We wished to design molecules, variations on the dithia-and diselenadiazolyl theme, with structural or electronic features incorporated into the exocyclic R-group that would promote the crystallization of uniformly spaced molecular then afford a half-filled energy band. There is, however, a 3.109 A) was long, and the radical association enthalpy in solution was weak (38). Later structural work on related derivatives (R = CF, (39), NMe, (40), and Me (41)) revealed other dimerization modes, e.g., 27, but afforded little encouragement that stacked structures were possible.…”

Section: Neutral Radical Molecular Conductorsmentioning

confidence: 99%

1993 ALCAN Award Lecture Chemical binding within and between inorganic rings; the design and synthesis of molecular conductors

Oakley¹

1993

Can. J. Chem.

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For a given number of skeletal atoms, the π-electron count of an unsaturated heterocycle can be modified by the incorporation of heteroatoms from different periodic groups. Sulfur and nitrogen are particularly effective in this regard, as their high electronegativity can stabilize electron-rich π-systems. A variety of aromatic, anti-aromatic, and radical systems can be prepared from admixtures of these elements. While the properties of these ring systems are interesting in their own right, the compounds are not without relevance in the design of new materials. The strong interannular interactions that are developed between these rings in the solid state makes them ideal candidates for the fabrication of molecular conductors. The origins and development of this area of research are the subjects of this presentation.

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Cyclic and Heterocyclic Thiazenes

Oakley

1988

Progress in Inorganic Chemistry

127

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Scheme I1A second binary compound, tetrasulfur dinitride (S4N2, 4), was also isolated before the end of the last century (32). Its correct elemental composition, however, was not established until 1925 (33), and its molecular formula not confirmed until 1951 (34). Early estimates suggested the formula N2Sj (32), an observation that attests to the tendency of the molecule to disproportionate above its melting point of 22.5"C (hence, the high sulfur content). The six-membered ring structure with a half-chair conformation was finally confirmed in 1981 (35,36). Most early preparative methods involved a thermal decomposition, for example, of S4N, in the presence of sulfur and/or carbon disulfide (37,38). More recently the use of simple metathetical reactions, for example, between Ni(S2N2H)? and S2CI2 has been explored (39). A simple procedure involving the reaction of aqueous ammonia with sulfur monochloride has also been developed (40); although the yield is low (<2%), the method provides a convenient preparation of small quantities (<0.5 g) starting from commercially available materials (3%). The solid state polymerization of S4N2 to (SN), ( 5 ) has recently been reported (36); this process is presumably initiated by trace amounts of (radical) impurities since, when recrystallized from diethyl ether, solid S,N, is indefinitely stable below its melting point (3%).Disulfur dinitride (6) (Scheme 11) was first generated (inadvertently) by Burt in 1910 (41) during an attempt to remove sulfur impurities from SJNJ by passing a vaporous mixture of the two over finely divided silver. At the time he noted the formation of a blue film [later characterized as (SN), polymer]. This reaction has been studied extensively since then, and now 304 RICHARD T. OAKLEY

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Electron spin resonance study of CH₃CNSSN˙, C₆H₅CNSSN˙, and SNSSN˙⁺free radicals

Cited by 99 publications

References 2 publications

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)

1993 ALCAN Award Lecture Chemical binding within and between inorganic rings; the design and synthesis of molecular conductors

Cyclic and Heterocyclic Thiazenes

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Electron spin resonance study of CH3CNSSN˙, C6H5CNSSN˙, and SNSSN˙+free radicals

Cited by 99 publications

References 2 publications

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se3–nSnN2+ (n = 0–3)

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se3–nSnN2+ (n = 0–3)

1993 ALCAN Award Lecture Chemical binding within and between inorganic rings; the design and synthesis of molecular conductors

Cyclic and Heterocyclic Thiazenes

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Electron spin resonance study of CH₃CNSSN˙, C₆H₅CNSSN˙, and SNSSN˙⁺free radicals

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)

A comparative electron spin resonance study of the selenothiadiazolyl radicals cyclo-Se_3–nS_nN₂⁺ (n = 0–3)