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).

Cocrystallization of the dithiadiazolyl (DTDA) radicals p-XC 6 F 4 CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p-XC 6 F 4 CNSSN] 2 [TEMPO] (1-5) whose structures all reflect a common S 4 •••O supramolecular motif.The nature of this interaction was probed by DFT calculations (M06/aug-cc-pVDZ) on 1 which revealed that the enthalpy of formation of the [C 6 F 5 CNSSN] 2 [TEMPO] supramolecular motif from [C 6 F 5 CNSSN] 2 and TEMPO is substantial (À 54.0 kJ mol À 1 ). Electronic structure calculations revealed a TEMPO-based doublet S = 1 = 2 configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is + 78.9 kJ mol À 1 higher in energy. An atoms-in-molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2-5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN•••SÀ S synthon is sacrificed in order to form the new S 4 •••O interaction.

Inclusion chemistry of dithiadiazolyl and diselenadiazolyl radicals into the MIL-53(Al) host occurs via vapor phase diffusion.

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Coordination of the dithiazolyl radical MBDTA leads to strong intramolecular metal–radical magnetic exchange but the strength of the intermolecular exchange coupling is strongly dependent on molecular packing.

SOMO Wrestling Molecules of C6F5CNSSN and TEMPO radicals tangle on the Dohyō. In their Communication on page 1371, J. M. Rawson and co‐workers implement favorable electrostatic contacts to drive cocrystal formation between different radicals. The concept is exemplified through the preparation and structural characterization of three sets of radical cocrystals: the 2:2 cocrystal [PhCNSSN]2[MBDTA]2 and the 2:1 cocrystals [C6F5CNEEN]2[TEMPO] (E=S, Se).

Beim SOMO‐Ringen steigen C6F5CNSSN‐ und TEMPO‐Radikale in den Ring. In ihrer Zuschrift auf S. 1385 setzen J. M. Rawson und Mitarbeiter vorteilhafte elektrostatische Kontakte ein, um die Kokristallbildung zwischen unterschiedlichen Radikalen zu fördern. Das Konzept wird am Beispiel der Herstellung und strukturellen Charakterisierung dreier Radikal‐Kokristalle demonstriert: des 2:2‐Kokristalls [PhCNSSN]2[MBDTA]2 und der 2:1‐Kokristalle [C6F5CNEEN]2[TEMPO] (E=S, Se).