On the Design of Radical–Radical Cocrystals

Formation of radical–radical cocrystals is an important step towards the design of organic ferrimagnets. We describe a simple approach to generate radical–radical cocrystals through the identification and implementation of well‐defined supramolecular synthons which favor cocrystallization over phase...

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Bibliographic Details
Published in:Angewandte Chemie 2019-01, Vol.131 (5), p.1385-1389
Main Authors: Nascimento, Mitchell A., Heyer, Elodie, Clarke, Joshua J., Cowley, Hugh J., Alberola, Antonio, Stephaniuk, Nadia, Rawson, Jeremy M.
Format: Article
Language:English
Subjects:
Bifurcations
Chemistry
Cocrystallization
Dimers
Diselenadiazolyl
Dithiadiazolyl
Electronegativity
Ferrimagnetism
Ferrimagnets
Kokristalle
Organische Ferrimagnete
Phase separation
Structural analysis
TEMPO
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Summary:Formation of radical–radical cocrystals is an important step towards the design of organic ferrimagnets. We describe a simple approach to generate radical–radical cocrystals through the identification and implementation of well‐defined supramolecular synthons which favor cocrystallization over phase separation. In the current paper we implement the structure‐directing interactions of the E−E bond (E=S, Se) of dithiadiazolyl (DTDA) and diselenadiazolyl (DSDA) radicals to form close contacts to electronegative groups. This is exemplified through the preparation and structural characterization of three sets of radical cocrystals; the 2:2 cocrystal [PhCNSSN]2[MBDTA]2 (4) [MBDTA=methyl benzodithiazolyl] and the 2:1 cocrystals [C6F5CNEEN]2[TEMPO] (E=S, 5; E=Se, 6). In 4 the two types of radical are linked via bifurcated inter‐dimer δ+S⋅⋅⋅Nδ− interactions whereas 5 and 6 exhibit a set of five‐centre δ+E⋅⋅⋅Oδ− contacts (E=S, Se). SOMO‐Ringen: Die Kokristallisation von Radikalen erfordert, dass offenschalige Moleküle mit anderen Molekülen, nicht mit sich selbst interagieren. Dieser Prozess kann durch die sorgfältige Auswahl günstiger elektrostatischer Wechselwirkungen zwischen Molekülen angetrieben werden.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201812132