Inorganic Chemistry, Vol.57, No.6, 3144-3150, 2018
Wheel-like Ln(18) Cluster Organic Frameworks for Magnetic Refrigeration and Conversion of CO2
Two isostructural 2D MOFs ([Ln(7)(CDA)(6)(HCOO)(3)(mu(3)-OH)(6)(H2O)(8)](n), abbreviated as 1-Gd and 2-Dy) were successfully synthesized under solvothermal conditions. The self-assembly of lanthanide(III) nitrate and 1,1'-cyclopropane-dicarboxylic acid (H(2)CDA) resulted in wheel-like Ln(18) cluster second building units (SBU), which are further linked to six neighboring wheels to generate a 2D ordered honeycomb array. Both 1-Gd and 2-Dy exhibit high thermal stability and decompose above 330 degrees C. Moreover, they have good solvent stability in ten common solvents arid pH stability with pH values from 1 to 13. Magnetic studies reveal that 1-Gd exhibits weak antiferromagnetic coupling between adjacent Gd3+ ions and has a large magnetocaloric effect of 47.30 J kg(-1) K-1 (Delta H = 7.0 T at 2 K), while 2-Dy shows ferromagnetic interaction between adjacent Dy3+ ions. Interestingly, 1-Gd and 2-Dy can catalyze the cycloaddition of CO2 to epoxides under mild conditions and can be reused at least five rounds with negligible loss of catalytic performance.