Unraveling Halogen Effects in Supramolecular Polymerization.

Halogens play a crucial role in numerous natural processes and synthetic materials due to their unique physicochemical properties and the diverse interactions they can engage in. In the field of supramolecular polymerization, however, halogen effects remain poorly understood, and investigations have been restricted to halogen bonding or the inclusion of polyfluorinated side groups. Recent contributions from our group have revealed that chlorine ligands greatly influence molecular packing and pathway complexity phenomena of various metal complexes. These results prompted us to explore the role of the halogen nature on supramolecular polymerization, a phenomenon that has remained unexplored to date. To address this issue, we have designed a series of archetypal bispyridyldihalogen PtII complexes bearing chlorine (1), bromine (2), or iodine (3) and systematically compared their supramolecular polymerization in nonpolar media using various experimental methods and theory. Our studies reveal a remarkably different supramolecular polymerization for the three compounds, which can undergo two competing pathways with either slipped (kinetic) or parallel (thermodynamic) molecular packing. The halogen exerts an inverse effect on the energetic levels of the two self-assembled states, resulting in a single thermodynamic pathway for 3, a transient kinetic species for 2, and a hidden thermodynamic state for 1. This seesaw-like bias of the energy landscape can be traced back to the involvement of the halogens in weak N-H···X hydrogen-bonding interactions in the kinetic pathway, whereas in the thermodynamic pathway the halogens are not engaged in the stabilizing interaction motif but rather amplify solvophobic effects.