Characterizing hydrogen and tetrel bonds in clusters of CO2with carboxylic acids

Abstract

The interaction between carbon dioxide and planar carboxylic acids has been investigated through the analysis of the microwave spectrum of the acrylic acid·CO₂ complex and quantum chemical modeling of the R–COOH·(CO₂)_1,16 clusters, where R = H, CH₂CH. As regards the 1 : 1 compounds, two species, involving the s-cis and s-trans conformers of acrylic acid were observed. For both of them, a similar bidentate interaction arises between the carbonyl group of CO₂ and the carboxylic group of the organic acid, leading to the formation of a planar six-membered ring. The binding energy is estimated to be D_e ≃ 21 kJ mol⁻¹, 1/3 being the energy contributions of the tetrel to hydrogen bonds, respectively. In the 1 : 16 clusters, the ring arrangement is broken, allowing for the interaction of the acid with several CO₂ molecules. The CO₂ molecules completely surround formic acid, whereas, in the case of acrylic acid, they tend to avoid the allyl chain.