Reversible single-crystal-to-single-crystal transition in Gd() metal-organic frameworks induced by heat and solvents with a significant magnetocaloric effect

The design and synthesis of a Gd( iii ) metal-organic framework with the formula [Gd 4 (BTDI) 3 (DMF) 4 ] n ( JXUST-40 , H 4 BTDI = 5,5′-(benzo[ c ][1,2,5]thiadiazole-4,7-diyl)diisophthalic acid) are reported hererin. Interestingly, a reversible single-crystal-to-single-crystal transition between JXUST-40 and {[Gd 4 (BTDI) 3 (H 2 O) 4 ]·6H 2 O} n ( JXUST-40a ) was achieved under the stimulation of heat and solvents. Both JXUST-40 and JXUST-40a exhibited good stability when soaked in common solvents and aqueous solutions with pH values of 1-12. Magnetic studies showed that JXUST-40a has a larger magnetocaloric effect with -Δ S max m = 26.65 J kg −1 K −1 at 2 K and 7 T than JXUST-40 due to its larger magnetic density. Structural analyses indicated that the coordinated solvent molecules play a crucial role in the coordination environment around the Gd( iii ) ions and the change in the framework, ultimately leading to the changes in the pore size and magnetism between JXUST-40 and JXUST-40a . In addition, both isomorphic [Dy 4 (BTDI) 3 (DMF) 4 ] n ( JXUST-41 ) and {[Dy 4 (BTDI) 3 (H 2 O) 4 ]·6H 2 O} n ( JXUST-41a ) displayed slow magnetic relaxation behaviour. Triggered by heat and solvents, Gd( iii ) MOF undergo a SC-SC transition. JXUST-40a exhibits better stability and a larger magnetocaloric effect with −Δ S max m = 26.65 J kg −1 k −1 under a 7 T applied field.