Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr4)2[Fe2(Cl2An)3] (1-d; NPr4+ = tetra-n-propylammonium; Cl2An2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: A low-temperature (LT) phase [(Fe3+)2(Cl2An2-)(Cl2An3-)2]2-; an intermediate (IM) phase [(Fe2.5+)2(Cl2An2-)(Cl2An2.5-)2]2-; and a high-temperature (HT) phase [(Fe2+)2(Cl2An2-)3]2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework.
ASJC Scopus subject areas
- 化学 (全般)