화학공학소재연구정보센터
Inorganic Chemistry, Vol.59, No.6, 3619-3630, 2020
Effects of Mixed Valency in an Fe-Based Framework: Coexistence of Slow Magnetic Relaxation, Semiconductivity, and Redox Activity
A 2-D coordination framework, (NEt4)(2)[Fe-2(fan)(3)] (1.5-(acetone); H-2 fan = 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone), was synthesized and structurally characterized. The compound is structurally analogous to a formerly elucidated framework, (NEt4)(2)[Fe-2(can)(3)] (H-2 can = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone), and adopts a 2-D (6,3) topology with the symmetrical stacking of [Fe-2(fan)(3)](2-) sheets that are held in position by the NEt4+ cations between the sheets. The investigation of the dc and ac magnetic properties of 1.5(acetone) revealed ferromagnetic ordering behavior and slow magnetization relaxation, as evinced from ac susceptibility measurements. Furthermore, the exposure of 1.5(acetone) to air led to the formation of a heptahydrate 1.7H(2)O which displayed distinct magnetic properties. The study of the redox state and extent of delocalization in 1.5(acetone) was undertaken via crystallography, in combination with Mossbauer and vis-NIR spectroscopy, to reveal the mixed-valence and delocalized nature of the as-synthesized material. As a result, the conductivity studies conducted on a pressed pellet showed a relatively high conductivity of 1.8 x 10(-2) S cm(-1) (300 K). In order to compare structurally related anilate-based structures, a relationship among the redox state, spectroscopic properties, and electronic properties was elucidated in this work. A preliminary investigation of 1.5(acetone) as a candidate anode material in lithium ion batteries revealed a high reversible capacity of 676.6 mAh g(-1) and high capacity retention.