Structural control of dithiazolyl radicals: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N

Alberola, Antonio; Burley, J.; Collis, Rebecca J.; Less, Robert J.; Rawson, Jeremy M.

doi:10.1016/j.jorganchem.2006.12.020

Cited by 23 publications

(14 citation statements)

References 34 publications

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“…[28][29][30][31][32][33][34][35][36] Several other DTA derivatives exhibit spin-Peierls like behaviour. 37,38 Amongst these spin-transition dithiazolyls, TTTA has been most comprehensively studied and is presented as a case study in the next section.…”

Section: Spin-transition Radical Dimersmentioning

confidence: 99%

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Reversible Spin Pairing in Crystalline Organic Radicals

Rawson

Hayward

2013

Spin‐Crossover Materials

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The concept of high spin and low spin configurations in d-block complexes is taught in every undergraduate introduction to the coordination chemistry of the transition metals. In this situation the interplay between interelectron repulsion or 'pairing energy' (P E ) and crystal (ligand) field splitting ( ) determines the electronic structure and provides an elegant example of how chemical tuning and modification of the ligand donor set can manipulate electronic structure. When is of a similar magnitude to P E then there is a fine balance between crystal field stabilisation energy (an enthalpic term which favours the low spin configuration) and maximising the number of microstates (an entropic term which favours the high spin configuration). In these cases spin-transitions typically occur between a low temperature enthalpically stabilised low spin configuration and a high temperature entropically favoured high spin configuration. The ability to drive spin-transitions thermally, through light-irradiation or pressure-induced transitions are the focus of the rest of this book. In this chapter we consider organic 'spin-transition' materials whose electronic structures can be manipulated in a conceptually similar but substantially different chemical fashion, that is by examining the fine interplay between inter-electron repulsion (P E ) and promotion energy to a low-lying vacant orbital ( ) within the context of organic chemistry.In order to understand the behaviour of such systems we shall begin with a discussion (Section 8.2) of stable free-radicals and their tendency to associate to form dimers, focusing on computational and experimental studies of the electronic structures of these dimers in the gas phase and in solution. In Section 8.3 we extend these discussions to the solid state and investigate examples in which we observe (i) thermal population of electronic excited states leading to a gradual thermal evolution of paramagnetism upon warming and (ii) firstorder solid state phase transitions in which bond cleavage can lead to abrupt diamagnetic-paramagnetic phase Spin-Crossover Materials: Properties and Applications, First Edition. Edited by Malcolm A. Halcrow.

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Section: Spin-transition Radical Dimersmentioning

confidence: 99%

“…Whilst neutral organic molecules tend to favour herringbone motifs, 46 the inclusion of electronegative atoms in the molecular backbone of DTAs appears to favour the layer-like motifs desirable for spin-transition properties. [31][32][33][34][35] …”

Section: Summary and Future Perspectivesmentioning

confidence: 99%

Reversible Spin Pairing in Crystalline Organic Radicals

Rawson

Hayward

2013

Spin‐Crossover Materials

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“…Consequently, further cyclization of the 1,3,2-dithiazole ring is accompanied by the elimination of sulfonamide [46]. [4,49], c R = 4-CN [6], d R = 5-CN [50], e R = 4,5,6,7-F 4 [51], f R = 5,6-(MeO) 2 [8] 80a-f 68a-f…”

Section: Reactivity Of the 132-dithiazole Ringmentioning

confidence: 99%

Synthesis and reactivity of 1,3,2-dithiazoles (review)

Попов

Konstantinova

Ракитин

2011

Chem Heterocycl Comp

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“…159 Shortly thereafter Awaga 242 -and later Rawson 101 -reported the first example (radical 75) in which the bistable regime included ambient temperature, and several other derivatives exhibiting this unusual "spin transition" behavior have been discovered (Table 9.2). 160,162,243,244 Further investigations into 75 have demonstrated that the bistability can be induced by photolysis, 245 and that application of external pressure shifts both of the transitions to higher temperatures. 246 As an illustrative example, Figure 9.28 shows the high and low temperature structures (both of which were solved at the same temperature (323 K), that is, within the bistable temperature window) and magnetic susceptibility for pyrazine-fused dithiazolyl radical 71.…”

Section: Magnetic Properties Of Thiazyl Radical-based π Dimers and π mentioning

confidence: 99%

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

Hicks

2010

Stable Radicals

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Structural control of dithiazolyl radicals: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N

Cited by 23 publications

References 34 publications

Reversible Spin Pairing in Crystalline Organic Radicals

Reversible Spin Pairing in Crystalline Organic Radicals

Synthesis and reactivity of 1,3,2-dithiazoles (review)

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

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