Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes

This paper refines the nature of the interactions between electron-deficient arenes and halide
anions. Conclusions are based on (i) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (ii) evaluation of crystal structures found in the Cambridge
Structural Database, and (iii) MP2/aug-cc-pVDZ calculations of F-, Cl-, and Br- complexes with TCB,
1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the π
system, the results establish that three distinctly different types of complexes are possible:  strongly covalent
σ complexes, weakly covalent donor−π-acceptor complexes, and noncovalent anion−π complexes. When
aryl C−H groups are present, a fourth type of interaction leads to C−H · · · X- hydrogen bonding.
Characterization of the different geometries encountered with the four possible binding motifs provides
criteria needed to design host architectures containing electron-deficient arenes.