Electrides: Early Examples of Quantum Confinement

Abstract

Electrides are ionic solids with cavity-trapped electrons, which serve as the anions. Localization of electrons in well-defined trapping sites and their mutual interactions provide early examples of quantum confinement, a subject of intense current interest. We synthesized the first crystalline electride, Cs(+)(18-crown-6)(2)e(-), in 1983 and determined its structure in 1986; seven others have been made since. This Account describes progress in the synthesis of both organic and inorganic electrides and points to their promise as new electronic materials. Combined studies of solvated electrons in alkali metal solutions and the complexation of alkali cations by crown ethers and cryptands made electride synthesis possible. After our synthesis of crystalline alkalides, in which alkali metal anions and encapsulated alkali cations are present, we managed to grow crystalline electrides from solutions that contained complexed alkali cations and solvated electrons. Electride research is complicated by thermal instability. Above approximately -30 degrees C, trapped electrons react with the ether groups of crown ethers and cryptands. Aza-cryptands replace ether oxygens with less reactive tertiary amine groups, and using those compounds, we recently synthesized the first room-temperature-stable organic electride. The magnetic and electronic properties of electrides depend on the geometry of the trapping sites and the size of the open channels that connect them. Two extremes are Cs(+)(15-crown-5)(2)e(-) with nearly isolated trapped electrons and K(+)(cryptand 2.2.2)e(-), in which spin-pairing of electrons in adjacent cavities predominates below 400 K. These two electrides also differ in their electrical conductivity by nearly 10 orders of magnitude. The pronounced effect of defects on conductivity and on thermonic electron emission suggests that holes as well as electrons play important roles. Now that thermally stable organic electrides can be made, it should be possible to control the electron-hole ratio by incorporation of neutral complexant molecules. We expect that in further syntheses researchers will elaborate the parent aza-cryptands to produce new organic electrides. The promise of electrides as new electronic materials with low work functions led us and others to search for inorganic electrides. The body of extensive research studies of alkali metal inclusion in the pores of alumino-silicate zeolites provided the background for our studies of pure silica zeolites as hosts for M(+) and e(-) and our later use of nanoporous silica gel as a carrier of high concentrations of alkali metals. Both systems have some of the characteristics of inorganic electrides, but the electrons and cations share the same space. In 2003, researchers at the Tokyo Institute of Technology synthesized an inorganic electride that has separated electrons and countercations. This thermally stable electride has a number of potentially useful properties, such as air-stability, low work function, and metallic conductivity. Now that both organic and ...

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“…The loosely bound anionic electrons are independent of any particular atoms or molecular in the lattices. Since first crystalline organic electride of Cs + (18‐crown‐6) 2 e − was synthesized by Ahmed et al in 1983,1 many attempts have been made to obtain the stable organic electrides to further understand the nearly‐free electron behaviors and their geometrical topologies. The discovery of room‐temperature stable inorganic electride [Ca 24 Al 28 O 64 ] 4+ ·4e − (C12A7)2 has drawn much attention to electride materials due to the promising practical applications and the substantial amounts of studies have been carried out to find new electrides 3.…”

Pressure-stabilized lithium caesides with caesium anions beyond the −1 state

“…However, alkali metals may also exhibit an atypical charge state of À 1 in a class of compounds called alkalides. These unusual compounds contain alkali metal anions as well as alkali cations embedded in organic molecules such as cryptands or crown ethers [3][4][5][6][7] . The unique oxidation states are related to another class of materials called electrides 6,[8][9][10][11][12] .…”