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On the Design of Radical–Radical Cocrystals
Author(s) -
Nascimento Mitchell A.,
Heyer Elodie,
Clarke Joshua J.,
Cowley Hugh J.,
Alberola Antonio,
Stephaniuk Nadia,
Rawson Jeremy M.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201812132
Subject(s) - cocrystal , synthon , radical , chemistry , dimer , supramolecular chemistry , crystallography , stereochemistry , molecule , crystal structure , organic chemistry , hydrogen bond
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 [C 6 F 5 CNEEN] 2 [TEMPO] (E=S, 5 ; E=Se, 6 ). In 4 the two types of radical are linked via bifurcated inter‐dimer δ+ S⋅⋅⋅N δ− interactions whereas 5 and 6 exhibit a set of five‐centre δ+ E⋅⋅⋅O δ− contacts (E=S, Se).