A pinboard by
Airi Kawamura

PhD Candidate, University of Chicago


My research investigates redox activity (i.e. the ability to remove or add electrons) of porous materials. These inorganic-organic hybrid materials have intrinsically large surface area due to the design of their framework structures that feature metal atoms or clusters linked by rigid organic molecules. Redox chemistry is route by which interesting magnetic and electronic properties may be instilled in these materials. For example, magnetic coupling and electrical conductivity have been reported in redox active metal organic frameworks. Porous materials with these properties may be useful for a variety of applications, including hybrid sensors, batteries and thermoelectric devices, among others. The work I will be presenting on focuses on sulfur-based organic molecules which link paramagnetic metal (i.e. metal atoms with unpaired electrons) sites to form a framework material. Redox activity may be possibly at both the metal and organic sites of the framework, allowing for tunability of the material's properties.


2D Conductive Iron-Quinoid Magnets Ordering up to Tc = 105 K via Heterogenous Redox Chemistry.

Abstract: We report the magnetism and conductivity for a redox isomeric pair of iron-quinoid metal-organic frameworks (MOFs). The oxidized isomer, (Me2NH2)2[Fe2L3]·2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) was previously shown to magnetically order below 80 K in its solvated form, with the ordering temperature decreasing to 26 K upon desolvation. Here, we demonstrate this compound to exhibit electrical conductivity values up to σ = 1.4(7) × 10(-2) S/cm (Ea = 0.26(1) cm(-1)) and 1.0(3) × 10(-3) S/cm (Ea = 0.19(1) cm(-1)) in its solvated and desolvated forms, respectively. Upon soaking in a DMF solution of Cp2Co, the compound undergoes a single-crystal-to-single-crystal one-electron reduction to give (Cp2Co)1.43(Me2NH2)1.57[Fe2L3]·4.9DMF. Structural and spectroscopic analysis confirms this reduction to be ligand-based, and as such the trianionic framework is formulated as [Fe(III)2(L(3-•))3](3-). Magnetic measurements for this reduced compound reveal the presence of dominant intralayer metal-organic radical coupling to give a magnetically ordered phase below Tc = 105 K, one of the highest reported ordering temperatures for a MOF. This high ordering temperature is significantly increased relative to the oxidized compound, and stems from the overall increase in coupling strength afforded by an additional organic radical. In line with the high critical temperature, the new MOF exhibits magnetic hysteresis up to 100 K, as revealed by variable-field measurements. Finally, this compound is electrically conductive, with values up to σ = 5.1(3) × 10(-4) S/cm with Ea = 0.34(1) eV. Taken together, these results demonstrate the unique ability of metal-quinoid MOFs to simultaneously exhibit both high magnetic ordering and high electrical conductivity.

Pub.: 24 Feb '17, Pinned: 28 Jun '17