A Dicobalt(II) Single-Molecule Magnet via a Well-Designed Dual-Capping Tetrazine Radical Ligand

The recent years have witnessed the glory development for the construction of high-performance mononuclear single molecule magnets (SMMs) within a specific coordination geometry, which, however, is not well applied in cluster-based SMMs due to the synthetic challenges. Given that the monocobalt­(II) complexes within a trigonal-prismatic (TPR) coordination geometry have been classified as excellent SMMs with huge axial anisotropy (D ≈ −100 cm^–1), here we designed and synthesized a new dual-capping tetrazine ligand, 3,6-bis­(6-(di­(1H-pyrazol-1-yl)­methyl)­pyridin-2-yl)-1,2,4,5-tetrazine (bpptz), and prepared a novel dicobalt­(II) complex, [Cp₂Co^III]­[{(hfac)­Co^II}₂(bpptz^•–)]­[hfac]₂·2Et₂O (1, hfac = hexafluoro­acetylacetonate). In the structure of 1, the bpptz^•– radical ligand enwraps two Co­(II) centers within quasi-TPR geometries, which are further bridged by the tetrazine radical in the trans mode. The magnetic study revealed that the interaction between the Co centers and the tetrazine radical is strongly antiferromagnetic with a coupling constant (J) of −65.8 cm^–1 (in the −2J formalism). Remarkably, 1 exhibited the typical SMM behavior with an effective energy barrier of 69 cm^–1 under a 1.5 kOe dc field, among the largest for polynuclear transition metal SMMs. In addition, DFT and ab initio calculations suggested that the presence of a strong Co­(II)–radical magnetic interaction effectively quenches the QTM effect and enhances the barrier height for the magnetization reversal.