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Abstract
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Using high-level ab initio calculations, the cooperativity effects between an aerogen-bonding and a pnicogen- or chalcogen-bonding interactions are studied in ternary Y ··· PH2CN ··· ZO3 and Y ··· SHCN ··· ZO3 complexes ( Y = NH3, N2 and Z = Ar, Kr, Xe). A detailed analysis of the structures, interaction energies and bonding properties is performed on these systems. For each set of the complexes, a favourable cooperativity is observed between Z ··· N and P/S ··· N interactions, especially in complexes involving NH3 and XeO3 molecules. It is found that for a given Y or Z, the amount of cooperativity effects in Y ··· PH2CN ··· ZO3 complexes are important than Y ··· SHCN ··· ZO3 ones. For each ternary complex considered, the effect of a Z ··· N aerogen bond on a P/S ··· N bond is more pro- nounced than that of a P/S ··· N bond on a Z ··· N bond. The mechanism of the cooperativity effects in the ternary complexes is studied by electron density difference, quantum theory of atoms in molecules and natural bond orbital analyses. The solvent effects are also studied on the interaction energy and cooperativity of Z ··· N and P/S ··· N bonds in the ternary systems.
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