In the past several decades, the field of cocrystal engineering has developed into a vital research topic in supramolecular chemistry, holding the foremost scope in crystal engineering, medicinal chemistry, materials chemistry, and the pharmaceutical industry. The medium of cocrystallization has been through the classic non-covalent interactions. However, cocrystallization through sigma hole (σ-hole)-based modern interactions is a breakthrough in crystal engineering. This σ-hole mediated non-covalent interaction uniquely contributes to supramolecular chemistry through different subgroups halogen bonding (XB), chalcogen bonding (ChB), pnictogen bonding (PnB), and tetrel bonding (TB). Despite much potential, chalcogen bonding, pnictogen bonding, and tetrel bonding are yet at an infancy stage compared to halogen bonding. Hence, we attempted to address the great potential of these non-covalent interactions (intra- and inter-molecular) and enlighten the ChB, PnB, and TB, as their outstanding contribution to the supramolecular domain needs to be communicated. Through this account, we promote these cooperative σ-hole-based interaction synthons as attractive toolboxes in supramolecular chemistry by addressing the strength and directionality of σ-hole potential, the role of steric hindrance, different modes of characterizations, application in distinct fields, etc. We hope this work will be the medium of a new direction in advancing σ-hole-assisted interactions in different research areas. Also, chalcogen, pnictogen, and tetrel bonding could get out of the shadow of halogen bonding and get their recognition in supramolecular chemistry.

中文翻译：

---

揭示西格玛空穴辅助共结晶的潜力：强调最新进展


在过去的几十年里，共晶工程领域已发展成为超分子化学的一个重要研究课题，在晶体工程、药物化学、材料化学和制药工业中占据着最重要的地位。共结晶的介质是通过经典的非共价相互作用。然而，通过基于西格玛孔（σ-hole）的现代相互作用进行共晶是晶体工程的突破。这种 σ 空穴介导的非共价相互作用通过不同的亚组卤素键合 (XB)、硫族键合 (ChB)、磷元素键合 (PnB) 和四元素键合 (TB) 对超分子化学做出独特贡献。尽管潜力很大，但与卤素键合相比，硫族键合、磷族键合和四元素键合仍处于起步阶段。因此，我们试图解决这些非共价相互作用（分子内和分子间）的巨大潜力，并启发 ChB、PnB 和 TB，因为它们对超分子领域的杰出贡献需要得到传达。通过这个帐户，我们通过解决σ-空穴势的强度和方向性、空间位阻的作用、不同的表征模式、在不同领域的应用等，将这些基于协同σ-空穴的相互作用合成子推广为超分子化学中有吸引力的工具箱我们希望这项工作能够成为在不同研究领域推进 σ 空穴辅助相互作用的新方向。此外，硫族键、磷族键和四元键也可以摆脱卤素键的阴影，并在超分子化学中得到认可。