Interplay between non-covalent interactions in 1D supramolecular polymers based on 1,4-bis(iodoethynyl)benzene

A study of the solution-phase, solid-state structures of halogen-bonded co-crystals of 1,4-bis(iodoethynyl)benzene (p-BIB) with three salts, namely, decyltrimethylammonium bromide (DTMABr), tetrapropylammonium bromide (TPABr), and tetrabutylammonium bromide (TBABr), has been carried out, along with theoretical calculations. Isothermal titration calorimetry (ITC) showed that the binding constant of bromide with p-BIB in THF is not strongly dependent on the cation, and that the entropic term clearly dominates the enthalpic one in the free energy of binding. In the three crystal structures, the bromide anion acts as a doubly connected node for halogen bonding interactions, which results in linear or angular open chains. The intrachain angles (IBr^-I) of the 1D supramolecular polymers based on p-BIB depend on the geometry and size of the cation and vary from 180° for DMTABr to 75° for TBABr. Non-covalent interaction (NCI) analysis of selected motifs and optimized crystals demonstrates that the balance between halogen bonds, hydrogen bonds, and van der Waals interactions, especially type-I halogenhalogen contacts, determines the crystal structures.