LAUSR

Traditional π‐covalent interactions have been proved in the non‐metal halogen bond adducts formed by chloride and halogenated triphenylamine‐based radical cations. In this study, we have rationally designed two metal‐involving halogen bond adducts with π‐covalency property, such as [L1‐Pd···I‐PTZ]+ (i.e., 1) and [L2‐Pd···I‐PTZ]+ (i.e., 2), in which the square‐planar palladium complexes serve as halogen bond acceptor and 3,7‐diiodo‐10H‐phenothiazine radical cation (i.e., [I‐PTZ]•+) acts as halogen bond donor. Noncovalent interaction analysis and quantum theory of atoms in molecules analysis revealed that there are notable halogen bond interactions along the Pd···I direction without genuine chemical bond formed in both designed adducts. Energy decomposition analysis together with natural orbital for chemical valence calculations were performed to gain insight into their bonding nature, which demonstrated the presence of remarkable π‐covalent interactions and σ‐covalent interactions in both 1 and 2. We therefore proposed a new strategy for building the metal‐involving halogen bonds with π‐covalency property, which will help the further development of new types of halogen bonds.