Molecular magnetism in nanodomains of isoreticular MIL-88(Fe)-MOFs

Abstract

Molecular magnetism in nanodomains of three isoreticular MIL-88(Fe) analogues is studied and reported. Microstructures of isoreticular extended frameworks of MIL-88B, MIL-88C, and the interpenetrated analogue of MIL-88D, i.e., MIL-126, with the trigonal prismatic 6-c acs net are synthesized by linking Fe₃O inorganic cluster units with organic carboxylate linkers – benzene-1,4-dicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC), and biphenyl-4,4′-dicarboxylic acid (BPDC), using a controlled solvent driven self-assembly process followed by a solvothermal method. The powder XRD traces are matched with the simulated diffraction patterns generated from their corresponding crystal structures, revealing the hexagonal symmetry for MIL-88B and MIL-88C, and the tetragonal symmetry for MIL-126. The elemental composition analysis confirms the empirical formula to be Fe₃O(L)₃ where L is the organic linker, supporting the formation of isoreticular MIL-88(Fe)-MOFs with MIL-88 topology. The morphologies of microstructures analyzed by SEM and TEM exhibit long spindle shaped rods with a core and a shell-like architecture for MIL-88B and MIL-88 C whereas MIL-126 shows cubic-shaped microstructures. The M–T plots confirm their blocking temperatures, T_B, to be 60 K, 50 K, and 40 K for MIL-88B, MIL-88C, and MIL-126, respectively. The M–H plots reveal their magnetic response to be ferromagnetic at 10 K with the coercivities, H_C, ranging from 250 G to 180 G. The gradual decrease in the T_B and H_C correlates with the nanocrystals’ domain size, which decreases from MIL-88B to MIL-88C to MIL-126. Their phase transition from the ferromagnetic state to the short range ordering of the superparamagnetic state is observed in the temperature range of 100 K to 300 K. At T > T_B, nanocrystals of all three MIL-88 microstructures act as a single-magnetic domain, owing to their shape anisotropy and finite-dimensionality. The electron density distribution and the spin density state modeled for each MIL-88 analogue exhibit localized electron density and spin density on Fe₃O clusters, indicating the short range magnetic moment ordering in triangular metal oxide nodes with no extended magnetic cooperativity from their organic linkers. The short-range ordering of superparamagnetism in MIL-88(Fe)-MOFs suggests their further study as porous molecular-based magnets.