Chirality Enhanced Halogen Bonding Cooperativity and Structural Stability of Two-Dimensional Iodinenes

Halogen
bond (XB), as a high-directional noncovalent
interaction,
is widely found and applied in many areas, such as chemistry, physics,
and material science. Recently, XB has been successfully utilized
to construct two-dimensional (2D) iodine networks, dubbed iodinenes.
However, the behavior of XB in such a single-element and periodic
system, which is constructed by XB networks between iodine molecules,
as well as the mechanism of stabilizing iodinene, have not been thoroughly
investigated. In this work, based on first-principles calculations,
we found that structural chirality can increase the cooperativity
of XB and preserve the directionality of XB in lattice vibration,
leading to the dynamic stability of iodinenes, while the mirror symmetry
has the opposite effect on the XB network. These results not only
extend our understanding of XB in iodinenes but also provide new insight
into studying the relationship between the chirality and stability
of XB in periodic systems.

卤键（Halogen Bond, XB）作为一种高方向性非共价相互作用，广泛存在并应用于化学、物理、材料科学等诸多领域。近年来，XB已被成功用于构建二维（2D）碘基网络，该网络被命名为碘烯（iodinenes）。然而，这种由碘分子间卤键网络构成的单元素周期性体系中卤键的行为，以及稳定碘烯的机制，尚未得到深入研究。本工作基于第一性原理计算（first-principles calculations）发现，结构手性可增强卤键的协同效应，并在晶格振动中维持卤键的方向性，从而赋予碘烯动态稳定性；而镜像对称（mirror symmetry）则对卤键网络产生相反的影响。上述研究结果不仅加深了我们对碘烯中卤键的认知，也为探究周期性体系中手性与卤键稳定性之间的关联提供了全新视角。