The reactivity of [Ar¹Ar²I](SCN) toward the solid-state arylation depends on the preorganization of halogen bond (XB)-bound SCN⁻: N-XB-bound thiocyanates, which, in contrast to N,S-XB-bound, undergoes the extremely rare N-arylation of SCN⁻.

We report a series of rotaxane‐based anion–π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.

The co‐crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co‐crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4‐MeC₆H₄Cl, 4‐MeC₆H₄Br, 4‐MeOC₆H₄Cl, 1,2‐Br₂C₆H₄) which were studied by X‐ray diffraction. In these systems, the strong collective effect of π⋅⋅⋅π stacking interactions and lone pair‐(X)⋅⋅⋅π‐hole‐(C) bondings between TCB and ArX promote the strength of X⋅⋅⋅N_cyanohalogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ‐hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ‐ hole‐(Cl) value (1.5 kcal/mol) in the haloarene 4‐MeOC₆H₄Cl (featuring an electron‐rich arene moiety and exhibiting very poor σ‐hole‐(Cl) ability) increases significantly in the stacked trimer (TCB)₂ ⋅ 4‐MeOC₆H₄Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅N_cyanoHaB strength for stacked trimers in comparison with parent unstacked haloarenes.

This manuscript reports a combination of crystallographic analysis (Cambridge Structural Database) and theoretical DFT calculations in chalcogen bonding interactions involving radicals in both the Ch bond (ChB) donor and acceptor. As a radical ChB acceptor (nucleophile) we have used benzodithiazolyl radical (BDTA) and as Ch bond donors (electrophile) we have used dithiadiazolyl and diselenadiazolyl radicals of the general formula p-X-C₆F₄–CNChChN (Ch = S, and Se). We have evaluated how the para substituent (X) affects the interaction energy, spin density and charge/spin transfer from the electron rich BDTA radical to the electron poor dichalcogenadiazolyl ring. The ability of the latter rings to form ChBs in the solid state has been examined by a comprehensive search in the CSD; several cases are used to exemplify the preferred geometric features of the complexes and they are compared with the theory. The molecular surface electrostatic potentials calculated for these ChB donors allow for a very precise rationalization of the self-assembly motifs most frequently adopted in the crystalline state and of their relative robustness.

A doubly-interlocked [2]catenane – or Solomon link – undergoes a complex conformational change upon addition of sulfate in methanol.