Activation of Small Molecules (H2, CO2, N2O, CH4, and C6H6) by a Porphyrinoid-Based Dimagnesium(I) Complex, an Electride

A density functional theory-based computation has been carried out to reveal the geometrical and electronic structures of Mg 2 EP ( 1 ), where EP is an extended (3.1.3.1) porphyrinoid system. EP is a 22 π electronic system and is aromatic in nature. Here, we have studied the thermodynamic and kinetic stabilities of EP 2- -supported Mg 2 2+ ion. The nature of bonding has been studied using natural bond orbital and atoms in molecule schemes. The presence of a covalent Mg(I)-Mg(I) σ-bond in Mg 2 EP is confirmed. The occurrence of a non-nuclear attractor (NNA) with large electron population, negative Laplacian of electron density at NNA, and presence of an electron localization function basin along with large nonlinear optical properties prompt us to classify Mg 2 EP as the first porphyrinoid-based organic electride. Further five small molecules, viz., dihydrogen (H 2 ), carbon dioxide (CO 2 ), nitrous oxide (N 2 O), methane (CH 4 ), and benzene (C 6 H 6 ), are found to be activated by the electron density between the two Mg atoms in Mg 2 EP.