Ultrasonic Clusterization Process to Prepare [(NNCO)6Co4Cl2] as a Novel Double-Open-Co4O6 Cubane Cluster: SXRD Interactions, DFT, Physicochemical, Thermal Behaviors, and Biomimicking of Catecholase Activity

Abderrahim Titi; Rachid Touzani; Anna Moliterni; Carlotta Giacobbe; Francesco Baldassarre; Mustapha Taleb; Nabil Al-Zaqri; Abdelkader Zarrouk; Ismail Warad

doi:10.1021/acsomega.1c07032

Ultrasonic Clusterization Process to Prepare [(NNCO)₆Co₄Cl₂] as a Novel Double-Open-Co₄O₆ Cubane Cluster: SXRD Interactions, DFT, Physicochemical, Thermal Behaviors, and Biomimicking of Catecholase Activity

ACS Omega. 2022 Sep 7;7(37):32949-32958. doi: 10.1021/acsomega.1c07032. eCollection 2022 Sep 20.

Authors

Abderrahim Titi¹, Rachid Touzani¹, Anna Moliterni², Carlotta Giacobbe³, Francesco Baldassarre², Mustapha Taleb⁴, Nabil Al-Zaqri⁵, Abdelkader Zarrouk⁶, Ismail Warad⁷

Affiliations

¹ Laboratory of Applied and Environmental Chemistry, Mohammed First University, Oujda60000, Morocco.
² Institute of Crystallography, CNR, Via Amendola, 122/O, Bari70126, Italy.
³ European Synchrotron Radiation Facility, 71 Avenue Des Martyrs, Grenoble38040, France.
⁴ Laboratory of Engineering, Organometallic, Molecular and Environment (LIMOME), Faculty of Science, Université Sidi Mohamed Ben Abdellah, Fez30000, Morocco.
⁵ Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh11451, Saudi Arabia.
⁶ Laboratory of Materials, Nanotechnology, and Environment, Faculty of Sciences, Mohammed V University in Rabat, P.O. Box 1014, Agdal-Rabat11000, Morocco.
⁷ Department of Chemistry, AN-Najah National University, P.O. Box 7, Nablus P400, Palestine.

Abstract

A novel double-open-cubane (NNCO)₆Co₄Cl₂ cluster with a Co₄O₆ core was made available under aqua-ultrasonic open atmosphere conditions for the first time. The ultrasonic clusterization of the (3,5-dimethyl-1H-pyrazol-1-yl)methanol (NNCOH) ligand with CoCl₂·6H₂O 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-Co₄O₆ cubane structure of the (NNCO)₆Co₄Cl₂ 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 Co₄O₆ core as a stable final product. The catalytic property of the (NNCO)₆Co₄Cl₂ 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).