This study marks chemical space available for pnictogen-bonding catalysis, and demonstrates that reactivity accessible in this space is unique.

X-ray crystallography data revealed the dichotomy of thiocyanate-involving noncovalent interactions in [Ar¹Ar²I](SCN), as reflected in the generation of two types of supramolecular aggregates: (i) previously unreported 4-membered heterotetramers (Ar¹/Ar² =...

The utilization of neutral receptors for the molecular recognition of anions based on chalcogen bonding (ChB) is an undeveloped area of host‐guest chemistry. In this manuscript, the synthesis of two new families of sulfur, selenium, and tellurium‐based ChB binding motifs are reported. The stability of the thiophene, selenophene, and tellurophene binding motifs has enabled the determination of the association constants for ChB halide anion binding in the polar aprotic solvent THF by 1H, 77Se, and 125Te NMR experiments. Two different aromatic cores are used and one or two Ch‐binding motifs are incorporated with the purpose of encapsulating the anion, offering up to two concurrent chalcogen bonds. Theoretical calculations and NMR experiments reveal that, for S and Se receptors, hydrogen‐bonding interactions involving the acidic H atom adjacent to the chalcogen atom are energetically favored over the ChB interaction. However, for the tellurophene binding motif, the σ‐hole interaction is competitive and more favored than the hydrogen bond.