Ligand-regulated unusual nickel clusters: A centrosymmetric dicubane Ni8 and a tetrahedral Ni10 cluster

Based on the reported Fe clusters constructed by using N -tris(hydroxymethyl)methylglycine (H 5 thmmg), herein, we explored the use of H 5 thmmg for Ni chemistry. Successfully, an octanuclear Ni cluster, Ni 8 O(H 3 thmmg) 6 •2NO 3 ( Ni 8 ) was acquired under solvothermal condition. Its metallic core is comprised of two centrosymmetric cubanes Ni 4 ( µ 3 -O) 3 ( µ 6 -O) linked by sharing an O 2− ion and six H 3 thmmg 2− ligands are attached to the periphery. Interestingly, the 2-mercapto-5-amino-1,3,4-thiadiazole (Hmat) ligand with both N and S donor atoms was introduced into the synthesis of Ni 8 cluster, a disparate decanuclear nickel cluster, Ni 10 O(OH) 2 (H 3 thmmg) 4 (mat) 8 ( Ni 10 ) is assembled by H 3 thmmg 2− and mat − mixed ligands. The metal core of Ni 10 cluster is a pudgy tetrahedron, whose four vertexes are four Ni 2+ ions and the remanent six Ni 2+ ions are located in the tetrahedral cavity. Four H 3 thmmg 2− ligands are located at the four vertices of the tetrahedron and 8 mat − ligands are all on the six sides of the tetrahedron. The different synthesis conditions contribute to the different configurations. Magnetic studies indicate that both complexes Ni 8 and Ni 10 display antiferromagnetic interactions. A Ni 8 cluster and a Ni 10 cluster were successfully acquired by regulating the ligands. The metallic core of Ni 8 cluster is comprised of two centrosymmetric cubanes Ni 4 ( µ 3 -O) 3 ( µ 6 -O). Interestingly, the mat − ligand was introduced into the synthesis of Ni 8 cluster and a new tetrahedral Ni 10 cluster was isolated.