A 2D Semiquinone Radical-Containing Microporous Magnet with Solvent-Induced Switching from Tc = 26 to 80 K
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- 作者：Ie-Rang Jeon ; Bogdan Negru ; Richard P. Van Duyne ; T. David Harris
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：December 23, 2015
- 年：2015
- 卷：137
- 期：50
- 页码：15699-15702
- 全文大小：318K
- ISSN：1520-5126
文摘
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 FeII affords the solid (Me2NH2)2[Fe2L3]·2H2O·6DMF. Analysis of X-ray diffraction, Raman spectra, and M?ssbauer spectra confirm the presence of FeIII centers with mixed-valence ligands of the form (L3)8– that result from a spontaneous electron transfer from FeII 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 N2 adsorption data of this activated compound gives a BET surface area of 885(105) m2/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.