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 ...

No abstract

Electrides are ionic compounds that have alkali metal cations complexed by a crown ether or cryptand, with trapped electrons as counterions. The crystal structures and properties of two electrides illustrate the diversity that is encountered. One Cs(+) (18-crown-6)(z)e(-), has relatively isolated, trapped electrons apparently centered at each anionic site. It has a low conductivity consistent with electron localization, with an activation energy for conductivity of at least 0.45 electron volt. The other, K(+) (cryptand[2.2.2])e(-), has electron pairs trapped in an elongated cavity in a singlet ground state, but there is also a thermally accessible paramagnetic state available. This electride is much more conducting, with an activation energy of only 0.02 electron volt.

Electrides are ionic compounds in which the cations are complexed by cryptands or crown ethers and the “anions” are trapped electrons. The crystal structures of five electrides are known and are similar to the corresponding alkalides (in which the anions are alkali metal anions) except that the anionic sites are “empty”. Theory and experiment strongly support a model in which the “excess” electrons are trapped in these anionic cavities and interact with each other through connecting channels, whose geometries vary significantly from one electride to another. Measurements of optical, alkali metal NMR, and EPR spectra, magnetic susceptibilities, and conductivities provide many data that can be correlated with the structures. Three electrides have essentially 1D chains of cavities connected by channels through which the electrons communicate, as indicated by magnetic susceptibilities that are well described by a 1D Heisenberg model. The electride, K+(cryptand[2.2.2])e- has a 2D array of cavities and channels. It appears that defects, probably missing electrons (holes), are responsible for its near-metallic conductivity. The fifth electride of known structure contains Cs+ complexed by a mixed sandwich of 15-crown-5 and 18-crown-6 and has a complex cavity−channel geometry, dominated by rings of six cavities. The arguments in favor of the proposed electride model, nearly-free electrons confined as a “lattice gas” in a complex array of cavities and channels, are presented in this paper.

An electride has been synthesized that is stable to auto-decomposition at room temperature. The key was the theoretically directed synthesis of a per-aza analogue of cryptand[2.2.2] in which each of the linking arms contains a piperazine ring. This complexant was designed to provide strong complexation of Na+ via pre-organization of a "crypt" that contains eight nonreducible tertiary amine nitrogens. The structure and properties indicate that, as with other electrides, the "anions" are electrons trapped in the cavities formed by close-packing of the complexed cations. The isostructural sodide, with Na- anions in the cavities, is also stable at and above room temperature.