Cesium(+1)(15-crown-5)2.cntdot.e-. A crystalline antiferromagnetic electride

Dawes, Steven B.; Eglin, Judith L.; Moeggenborg, Kevin; Kim, Jineun; Dye, James

doi:10.1021/ja00005a025

Cited by 64 publications

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“…Each anionic site in the electride is surrounded by eight nearest-neighbor complexed cesium cations, two each at distances of 6.92, 7.63, The properties of Cs+( 15 C 5 ) 2 e -confirm the localized nature of this electride. [29] As with Cs+(18C6)2e-, there is a pronounced effect on the conductivity as a result of Cs-doping. [57] Even with "undoped" samples, however, the X-band EPR spectrum shows the effects of exchange narrowing.…”

Section: -Localized Electridesmentioning

confidence: 98%

“…NMR studies, differential scanning calorimetry and magnetic susceptibilities all show that an endothermic phase transition occurs at 266K to give a less paramagnetic state. [29] This appears to be partial melting with considerable motion of the crown ether. Complete melting to give an unstable blue liquid occurs at -295 K.…”

Section: -Localized Electridesmentioning

confidence: 99%

“…The fact that a "spin-flop" occurs at 2 K with field strengths of 0.5 T shows that the magnetic anisotropy is weak. [29] Solid-state 133Cs NMR studies show that the electron density at Cs+ is higher than that in Cs+(l8C6)2e-, but it still has only 0.063 percent atomic character. NMR studies, differential scanning calorimetry and magnetic susceptibilities all show that an endothermic phase transition occurs at 266K to give a less paramagnetic state.…”

Section: -Localized Electridesmentioning

confidence: 99%

“…This view is strongly reinforced by the 133Cs NMR Knight shifts of Cs+ in C~+ ( l 8 C 6 )~e -and Csi( 1 5 C5)ze-. [29,48] These correspond to only 0.033 and 0.063 percent atomic character, respectively.…”

Section: -Electride-alkalide Structural Similaritiesmentioning

confidence: 99%

“…Three peaks occur at 900-950, 1250 and 1600-1700 nm rather than the single broad peak usually observed with localized electrides. [29] -The origin of the three peaks is not known, although it has been suggested that they might arise from non-degenerate transitions from the s-like ground state to three excited p-states. Because of the polycrystalline nature of the films and the unknown way in which crystallization occurs upon solvent evaporation, any explanation of the unusual optical spectrum of Cs+(15C5)2e-is tentative.…”

Section: -Localized Electridesmentioning

confidence: 99%

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Electrides and Alkalides - Comparison With Metal Solutions

Dye

1991

J. Phys. IV France

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-The similarities between species in ammonia, amine and ether solutions of the alkali metals and in crystalline alkalides and electrides is striking. In solution we can identify the species M+,olv, e-,,lV, M-, M+-e-, "e2"', and at high concentrations, e-conduction. In alkalides, electrides and mixed systems, species analogous to each of these can be found, in addition to alkali metal anion dimers, M=,olv, and chains, (M"-)". Since the last Colloque Weyl we have determined the crystal structures and properties of 30 alkalides and 4 electrides. Correlation of structures and properties can now be made and will be discussed. A potentially rich area of investigation is the solution and liquid-state chemistry of alkalides and electrides. It is likely that the compound L~( C H~N H Z )~, studied by Sienko and others some time ago in both the liquid (metallic) state and the solid (semiconductor?) state, is an electride. Analogous alkalides, such as L~+ ( H~N C H~C H Z N H~)~N~ Li+(CH3NH2)4Na-,Li+(C2H5NH2)4Na-can be prepared and it appears that other alkali metal anions can be used instead of Na-. The solubility and stability of alkalides and electrides dissolved in dimethyl ether suggest that these would be excellent systems for the study of the properties of alkali metal solutions. l -IntroductionElectrides and alkalides have much in common with alkali metal solutions in ammonia, amines, polyethers and other solvents.Not only are crystalline electrides and alkalides synthesized from metal solutions, but many of the same species that are used to explain solution properties are also present in the ionic crystals.[l] This paper reviews the evidence for various species in solution and uses the crystal structures and properties of electrides and alkalides to identify similar species in the solid state. The variety of packing geometries of the complexed cations (and in alkalides of the alkali metal anions) results in a number of interesting phenomena.For example, electrides exhibit electron localization, delocalization, spin-pairing and antiferromagnetism [ 2 ] ; and various alkalides contain separated alkali metal anions, cation-anion pairs, anion dimers and chains of anions.Article published online by EDP Sciences and available at http://dx

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Section: -Localized Electridesmentioning

confidence: 98%

Section: -Localized Electridesmentioning

confidence: 99%

Section: -Localized Electridesmentioning

confidence: 99%

Section: -Electride-alkalide Structural Similaritiesmentioning

confidence: 99%

Section: -Localized Electridesmentioning

confidence: 99%

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Electrides and Alkalides - Comparison With Metal Solutions

Dye

1991

J. Phys. IV France

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Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Leung

2005

Encyclopedia of Inorganic Chemistry

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This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 1993. The advancement in instrumentation and spectroscopic techniques in the past decade has provided the researchers with more powerful tools for structure determination of compounds. In this respect, alkalides containing mixed‐sandwich complexes of alkali metal cations, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalating in zeolite, and interstitial hydride enclosed by an unusual (Li + ) 8 cubic cage have been found or studied by NMR. With the successful preparation of Na 3 N recently, its correct structure has been revealed. The exact composition of ‘NaB 6 ’ has also been determined. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been demonstrated. Trimetallic Li‐Na‐K amides, alkoxide compounds, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides have been reported.

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Reactions to Form Electrides

Atwood¹

1998

Inorganic Reactions and Methods

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Cesium(+1)(15-crown-5)2.cntdot.e-. A crystalline antiferromagnetic electride

Cited by 64 publications

References 0 publications

Electrides and Alkalides - Comparison With Metal Solutions

Electrides and Alkalides - Comparison With Metal Solutions

Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Reactions to Form Electrides

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