Paramagnetic liquids: the preparation and characterisation of the thermally stable radical Bu^tCNSNS· and its quantitative photochemically symmetry allowed rearrangement to a second stable radical Bu^tCNSSN

Abstract

The new thermally stable paramagnetic liquid 5-t-butyl-l,3,2,4-dithiadiazolyI has been isolated in the dark and quantitatively photochemically isomerised to the paramagnetic liquid 5-t-butyl-2,3,1,4-dithiadiazolyl (non-systematic numbering for ease of comparison).Thermally stable, neutral, free-radical, non-metal compounds can be categorised by the state of lowest energy in which they remain substantially paramagnetic. (i) Paramagnetic solids: t radicals which are paramagnetic in all states. These include the sterically hindered radicals such as diphenylpicrylhydrazyl (DPPH),3 (C6C15)3C,4 and the non-sterically hindered 0 2 and C102.5 (ii) Paramagnetic liquids: radicals which are diamagnetic dimers in the solid state but are extensively dissociated upon melting, e.g. But2N0,6 (CF3)2N0,7 and C F 3 m C F 3 . g (iii) Paramagnetic gases: radicals which are t There are a number of examples of ionic paramagnetic solids, e.g.

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

“…For organic systems, however, only a few materials have been known as paramagnetic liquids. The neutral radicals, dithiazolyl or dithiadiazolyl compounds (Table 29), [879][880][881][882] form a liquid state at RT, but it is readily expected that the neutral radical liquids do not show an effective electric conductivity.…”

The preparation and X-ray crystal structure of Te(N3)3SbF6 containing the triazidotellurium(IV) cation, Te(N3)3+

“…The S2N+ cation, in S2NAsF6 (1) has a rich chemistry, and is an important building block in the systematic synthesis of other sulfur-nitrogen-containing compounds (2)(3)(4)(5)(6)(7)(8)(9). It would be of interest to prepare the selenium and tellurium analogues, Se2NAsF6 and Te2NAsF6, as they should also have extensive chemistries, because they are of interest in their own right and because very few isolated selenium-nitrogen or telluriumnitrogen species exist.…”

The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials

“…The feature of 1,3,2,4-dithiadiazolyl radicals 37 which has garnered the most attention is their thermal or photochemical rearrangement to the isomeric 1,2,3,5-radicals 35. The thermal reaction occurs in solution 120,143,145,146 and the solid state, 147 and can also be induced photochemically. 143,144 This transformation is most conveniently monitored in solution using EPR spectroscopy, although UV-Visible spectroscopy has also been employed.…”