Halogen Bond‐Involving Supramolecular Assembly Utilizing Carbon as a Nucleophilic Partner of I⋅⋅⋅C Non‐covalent Interaction

Abstract Co‐crystallization of 180°‐orienting σ‐hole‐accepting tectons, namely, 1,4‐diisocyanobenzene ( 1 ) and 1,4‐diisocyanotetramethylbenzene ( 2 ), with such homoditopic halogen bond donors as 1,4‐diiodotetrafluorobenzene (1,4‐FIB) and 4,4’‐diiodoperfluorobiphenyl (4,4’‐FIBP) afforded co‐crystals 1 ⋅ 1,4‐FIB, 1 ⋅ 4,4’‐FIBP, and 2 ⋅ 1,4‐FIB. Their solid‐state structures exhibit 1D‐supramolecular arrangements, which are based on poorly explored I⋅⋅⋅C halogen bonding; this study is the first in which the supramolecular assembly utilizing halogen bonding with a terminal C atom was performed. The use of the potentially tetrafunctional σ‐hole accepting tetraiodoethylene (TIE) leads to supramolecular architecture of a higher dimension, 3D‐framework, observed in the structure of 1 ⋅ TIE. DFT calculations, used to characterize the halogen bonding situation, revealed that the I⋅⋅⋅C non‐covalent interactions are moderately strong, ranging from −4.07 in 1 ⋅ TIE to −5.45 kcal/mol in 2 ⋅ 1,4‐FIB. The NBO analysis disclosed that LP(C)→σ* charge transfer effects are relevant in all co‐crystals.