Ultrasonic Clusterization Process to Prepare [(NNCO) 6 Co 4 Cl 2 ] as a Novel Double-Open-Co 4 O 6 Cubane Cluster: SXRD Interactions, DFT, Physicochemical, Thermal Behaviors, and Biomimicking of Catecholase Activity.

A novel double-open-cubane (NNCO) 6 Co 4 Cl 2 cluster with a Co 4 O 6 core was made available under aqua-ultrasonic open atmosphere conditions for the first time. The ultrasonic clusterization of the (3,5-dimethyl-1 H -pyrazol-1-yl)methanol (NNCOH) ligand with CoCl 2 ·6H 2 O salts in ethanol yielded a high-purity and high-yield cluster product. Energy-dispersive X-ray (EDX), Fourier transform infrared (FT-IR), and ultraviolet (UV)-visible techniques were used to elucidate the clusterization process. The double-open-Co 4 O 6 cubane structure of the (NNCO) 6 Co 4 Cl 2 cluster was solved by synchrotron single-crystal X-ray diffraction (SXRD) and supported by density functional theory (DFT) optimization and thermogravimetric/differential TG (TG/DTG) measurements; moreover, the DFT structural parameters correlated with the ones determined by SXRD. Molecular electrostatic potential (MEP), Mulliken atomic charge/natural population analysis (MAC/NPA), highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO), density of states (DOS), and GRD quantum analyses were computed at the DFT/B3LYP/6-311G(d,p) theory level. The thermal behavior of the cluster was characterized to support the formation of the Co 4 O 6 core as a stable final product. The catalytic property of the (NNCO) 6 Co 4 Cl 2 cluster was predestined for the oxidation process of 3,5-DTBC diol (3,5-di- tert -butylbenzene-1,2-diol) to 3,5-DTBQ dione (3,5-di- tert -butylcyclohexa-3,5-diene-1,2-dione).