A 2D Semiquinone Radical-Containing Microporous Magnet with Solvent-Induced Switching from Tc=26 to 80 K

The incorporation of tetraoxolene radical bridging ligands into a microporous magnetic solid is demonstrated. Metalation of the redox-active bridging ligand 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) with Fe-II affords the solid (Me2NH2)(2)[Fe2L3]center dot 2H(2)O center dot 6DMF. Analysis of X-ray diffraction, Raman spectra, and Mossbauer spectra confirm the presence of Fe-III centers with mixed-valence ligands of the form (L-3)(8-) that result from a spontaneous electron transfer from Fell to L2-. Upon removal of DMF and H2O solvent molecules, the compound undergoes a slight structural distortion to give the desolvated phase (Me2NH2)(2)-[Fe2L3], and a fit to N-2 adsorption data of this activated compound gives a BET surface area of 885(105) m(2)/g. Dc magnetic susceptibility measurements reveal a spontaneous magnetization below 80 and 26 K for the solvated and the activated solids, respectively, with magnetic hysteresis up to 60 and 20 K. These results highlight the ability of redox-active tetraoxolene ligands to support the formation of a microporous magnet and provide the first example of a structurally characterized extended solid that contains tetraoxolene radical ligands.