The construction of supramolecular aggregates based on halogen bonding (XB) are of considerable interest due to the fact that the synthesized systems exhibit a number of useful properties. A number of supramolecular XB tectons for the crystal engineering based on organic species and metal complexes were described earlier, however, squared-planar platinum(II) complexes are poorly studied in this way.
In our work, we showed that the [PtCl4]2– anion is able to act as an XB-acceptor with a neutral XB donor in the (PPN)2[PtCl4]•(1,4-C6F4I2) (PPN+ is Ph3P=N=PPh3+; 1,4-C6F4I2 is FIB) adduct, and in the salt (Ph3PCH2I)2[PtCl4] with a cation, which also incorporates an XB donor center. X-ray diffraction (SC-XRD) data were obtained and analyzed for these substances. XB of C-I∙∙∙I-Pt type was found in both structures base on the geometrical criteria. The existence of this bond was confirmed by appropriate theoretical calculations.