Demarcating Noncovalent and Covalent Bond Territories: Imine-CO₂ Complexes and Cooperative CO₂ Capture

Chemical bond territory is rich with covalently bonded molecules wherein a strong bond is formed by equal or unequal sharing of a quantum of electrons. The noncovalent version of the bonding scenarios expands the chemical bonding territory to a weak domain wherein the interplay of electrostatic and π-effects, dipole-dipole, dipole-induced dipole, and induced dipole-induced dipole interactions, and hydrophobic effects occur. Here we study both the covalent and noncovalent interactive behavior of cyclic and acyclic imine-based functional molecules (XN) with CO₂. All parent XN systems preferred the formation of noncovalent (nc) complex XN···CO₂, while more saturated such systems (XN') produced both nc and covalent (c) complexes XN'⁺-(CO₂)^-. In all such cases, crossover from an nc to c complex is clearly demarcated with the identification of a transition state (ts). The complexes XN'···CO₂ and XN'⁺-(CO₂)^- are bond stretch isomers, and they define the weak and strong bonding territories, respectively, while the ts appears as the demarcation point of the two territories. Cluster formation of XN with CO₂ reinforces the interaction between them, and all become covalent clusters of general formula (XN⁺-(CO₂)^-). The positive cooperativity associated with the NH···OC hydrogen bond formation between any two XN'⁺-(CO₂)^- units strengthened the N-C coordinate covalent bond and led to massive stabilization of the cluster. For instance, the stabilizing interaction between the XN unit with CO₂ is increased from 2-7 kcal/mol range in a monomer complex to 14-31 kcal/mol range for the octamer cluster (XN'⁺-(CO₂)^-)₈. The cooperativity effect compensates for the large reduction in the entropy of cluster formation. Several imine systems showed the exergonic formation of the cluster and are predicted as potential candidates for CO₂ capture and conversion.