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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Two-dimensional frameworks formed by pentagonal bipyramidal cobalt(ii) ions and hexacyanometallates:
1State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China. wangxy66@nju.edu.cn.
Abstract:
We herein report the syntheses, structures, and magnetic properties of two isostructural two-dimensional (2D) coordination polymers based on a pentagonal bipyramidal CoII unit [Co(TODA)]2+ and two hexacyanometallates, namely [MIII(CN)6]2[CoII(TODA)]3·9H2O (M = Cr (1), Co (2), TODA = 1,4,10-trioxa-7,13-diazacyclopentadecane). Structure analyses show that both complexes have 2D honeycomb structures where the [Co(TODA)]2+ units are bridged by the [MIII(CN)6]3- groups through three cyano groups in the facial positions. Magnetic investigation reveals ferromagnetic coupling between the CrIII and CoII centres through cyanides in 1. Due to the antiferromagnetic interaction between the layers, compound 1 exhibits an antiferromagnetic ordering below 11.4 K, and shows a metamagnetic phase transition under an external dc field. Due to the disorder of the TODA ligands, compound 1 shows a spin glass behavior, which leads to slow magnetic relaxation in 1. A butterfly-shaped hysteresis loop at 1.8 K can be observed with a coercive field of 720 Oe, which is quite large for cyano-bridged Cr-Co molecular magnets. For compound 2 containing the diamagnetic [CoIII(CN)6]3- unit, field-induced slow magnetic relaxation was also verified, which makes compound 2 a rare example of an SIM assembled in a 2D network. An easy-plane magnetic anisotropy with a positive D value (29.9 cm-1 by PHI and 26.5 cm-1 by Anisofit2.0) was deduced for hepta-coordinated CoII centers. These results show the efficiency of the strategy of combining cyanometallates and pentagonal bipyramidal precursors for novel molecular magnetic materials.
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