Chirality Enhanced\nHalogen Bonding Cooperativity and\nStructural Stability of Two-Dimensional Iodinenes

Halogen\nbond (XB), as a high-directional noncovalent\ninteraction,\nis widely found and applied in many areas, such as chemistry, physics,\nand material science. Recently, XB has been successfully utilized\nto construct two-dimensional (2D) iodine networks, dubbed iodinenes.\nHowever, the behavior of XB in such a single-element and periodic\nsystem, which is constructed by XB networks between iodine molecules,\nas well as the mechanism of stabilizing iodinene, have not been thoroughly\ninvestigated. In this work, based on first-principles calculations,\nwe found that structural chirality can increase the cooperativity\nof XB and preserve the directionality of XB in lattice vibration,\nleading to the dynamic stability of iodinenes, while the mirror symmetry\nhas the opposite effect on the XB network. These results not only\nextend our understanding of XB in iodinenes but also provide new insight\ninto studying the relationship between the chirality and stability\nof XB in periodic systems.