Tetrel bonds between PySiX3 and some nitrogenated bases: Hybridization, substitution, and cooperativity

• PySiX3 forms a tetrel bond with some nitrogenated bases.
• The strength of tetrel bond is affected by the substitution and hybridization effects.
• The tetrel bond is mainly governed by electrostatic and polarization interactions.
• The tetrel bond exhibits cooperative effects with triel bond.

Ab initio calculations have been performed to study the influence of hybridization, substitution, and cooperativity on the tetrel bond in the complexes of PySiX3 (Py = pyridine and X = halogen). The tetrel bond becomes stronger in the order of p-PySiF3⋯NCH(sp) < p-PySiF3⋯NHCH2(sp2) < p-PySiF3⋯NH3(sp3). The electron-donating group in the electron donor strengthens the tetrel bond, and this effect is mainly achieved through electrostatic and polarization interactions. Tetrel bonding displays cooperative effects with triel bonding and chalcogen bonding, characterized by shorter binding distances and greater electron densities. The cooperative effects between triel/chalcogen bond and tetrel bond have been analyzed by molecular electrostatic potentials and charge transfer. Energy decomposition indicates that many-body effects are mainly caused by polarization energy. The geometries of Si⋯N interaction and its applications in crystal materials have been characterized and evidenced by a CSD research.

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