Tuning the structure and magnetic properties via distinct pyridine derivatives in cobalt(II) coordination polymers

Precise modulation of the structure and magnetic properties of coordination compounds is of great importance in the development of framework magnetic materials. Herein, we report that the coordination self-assembly of a neutral cobalt(s) magnetic building block and selective pyridine derivatives as organic linkers has led to two distinct cobalt(s) coordination polymers, {Co(DClQ)(2)(bpy)}(n) (1) and {Co-2(DClQ))(4)(tpb)}(n) (2) (DClQ = (5,7-dichloro-8-hydroxyquinoline; bpy = 4, 4'-dipyridine; tpb = 1,2,4,5-tetra(4-pyridyl)benzene)). Structural analyses revealed that 1 and 2 are one-dimensional (1D) and 2D coordination polymers containing the same neutral magnetic building block (Co(DClQ)(2)] bridged by bitopic bpy and tetratopic tpb ligands, respectively. Both the complexes have a distorted octahedral CoN4O2 coordination geometry around each cobalt center offered by the bidentate ligand and organic linkers. Magnetic studies reveal large easy-plane and easy-axis magnetic anisotropy for 1 and 2, respectively. However, because of the weak antiferromagnetic coupling between the bpy-bridged Co-II centers, no slow relaxation of the magnetization was observed in 1 under both zero or applied dc fields. Interestingly, complex 2 exhibits slow magnetic relaxation under external fields, indicative of a framework single-ion magnet of 2. Theoretical calculations further support the experimental results and unveil that the D values are +65.3 and -91.2 cm(-1) for 1 and 2, respectively, while the magnetic exchange interaction was precisely estimated as -0.16 (1) and -0.009 (2) cm(-1). The foregoing results show that the structural dimensionality and magnetic properties can be rationally modified via pre-designed magnetic building blocks and a suitable choice of organic bridging ligands.

Automated summary

The precise modulation of the structure and magnetic properties of coordination compounds is crucial for the development of framework magnetic materials. In this study, the coordination self-assembly of a neutral cobalt(s) magnetic building block and selective organic linkers resulted in two distinct cobalt(s) coordination polymers with different magnetic anisotropy behaviors. The theoretical calculations supported the experimental results and provided insights into the magnetic exchange interaction and D values of the coordination polymers.