Optische Absorptions-Spektroskopie an ionischen Ozoniden

Assenmacher, Wilfried; Jansen, Martin

doi:10.1002/(sici)1521-3749(199804)624:4<661::aid-zaac661>3.0.co;2-0

Cited by 5 publications

(4 citation statements)

References 16 publications

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“…Thus for example, the bright orange-red to red alkaline and tetraalkylammonium ozonide salts are well-known and have recently been structurally and spectroscopically characterised. 31 The colour-determining broad band around 20(±1) 3 10 3 cm 21 (in solution at  21500 cm 21 and calculated 32 at 22300 cm 21 ) is found at a higher energy, by ≈ 4000 cm 21 , than the analogously assigned transition of S 3 2 in the blue sulfur ultramarines (see Section 2).…”

Section: Discussionmentioning

confidence: 80%

The nature of the chalcogen colour centres in ultramarine-type solids

Reinen¹,

Lindner²

1999

Chem. Soc. Rev.

138

119

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Blue minerals and gems have always been subjects of fascination to man. In particular lapislazuli is and was highly esteemed and also used as a precious stone and as a pigment. The host compound is the zeolite-type sodalite and the colour centres are S 2 2 and S 3 2 , whose amount ratio determines the specific hue, varying from violet blue to blue to green. But Se 2 2 can also be substituted into the sodalite cages in high percentages, giving the pigment a brilliant red colour. It is even possible to incorporate the rather voluminous radical species Te 2 and Te 2 2 into the sodalite matrix. Because the otherwise unstable colour centres are completely screened from the atmosphere and isolated from each other in the cages, they can be fully characterised by various spectroscopic techniques.

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Section: Discussionmentioning

confidence: 80%

The nature of the chalcogen colour centres in ultramarine-type solids

Reinen¹,

Lindner²

1999

Chem. Soc. Rev.

138

119

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“…The considerably broadened contours of the spectra of the solids as measured on single crystals in transmission or on powder in remission, indicate pronounced cooperative interactions. The absorption in solution can be attributed to isolated (solvatized) O 3 Ϫ anions, the vibronic fine structure being explicable only by vibrational transitions in an electronically excited state [26].…”

Section: Magnetic Measurementsmentioning

confidence: 99%

“…On one hand less polar reactants are often slightly soluble in this polar solvent, on the other hand due to its nucleophilicity, NH 3 strongly competes with the O 3 Ϫ anion for the electrophilic educts and thus hinders targeted reactions. Indeed, alkali metal ozonides are soluble in acetonitrile or DMSO, but such solutions decompose within a few minutes [26,30].…”

Section: Solubility and Reactivity Of Ionic Ozonidesmentioning

confidence: 99%

Ionic Ozonides

Jansen

Nuss

2007

Zeitschrift anorg allge chemie

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Ionic Ozonides [1] were mentioned for the first time during the second half of the nineteenth century. However, fundamental aspects of their chemistry and physics remained obscure until more recently procedures had been provided that allow for their syntheses in gram‐amounts, and in high purity. Respective preparative approaches start by reacting the alkali metal superoxides KO2, RbO2, or CsO2 with O2/O3 mixtures, at punctilious temperature control. Subsequently, the raw product is extracted with liquid ammonia. From the solution obtained, solid ozonides are harvested and purified by recrystallization. As rather versatile and efficient accesses to ozonides of further cations, metathesis reactions or cation exchange in liquid ammonia have been developed. The samples obtained have allowed for full structural and basic physical characterizations. All ionic ozonides known are metastable with respect to release of dioxygen, [NMe4]O3 being the most stable one (onset of rapid decomposition at 348 K). Depending on the respective crystal field, the bond lengths and angles of the ozonide anion vary significantly, and consistently, from 135 to 129 pm, and 113 to 120°, respectively. The magnetic moments of the paramagnetic O3− determined by susceptibility measurements (1.70–1.80 μB) deviate but slightly from the spin‐only value for one unpaired electron. This finding complies well with the small anisotropy of the g‐factors. As an achievement of possibly far reaching consequences, stable solutions of ionic ozonides in organic solvents have become available, opening the way to the use of O3− as a ligand, or synthon, in coordination and molecular chemistry.

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“…It therefore is a necessity for the development of the chemistry of the ozonide ion to have additional solvent systems available. The alkali metal ozonides can be dissolved in dry acetonitrile and dimethylsulfoxide, but the ozonide ion decomposes within minutes in these solvents [26,38,39]. Alkali metal ozonides can also be complexed with crown ethers [40], but, again, such solutions of potassium ozonide in benzene or toluene decompose within minutes at room temperature and within an hour at Ϫ30°C [41].…”

Section: Introductionmentioning

confidence: 99%

Dimeric Sandwich‐like Ion Pairs in the Crystal Structure of Tetrabutylammonium Ozonide Ammoniate

Dıetzel

Jansen

2006

Zeitschrift anorg allge chemie

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The novel ionic ozonide {[N(C 4 H 9 ) 4 ](O 3 )} 4 ·4.75NH 3 was synthesized by ion-exchange reaction in liquid ammonia. The crystal structure was determined by single crystal diffraction at 100 K (monoclinic space group P2 1 , a ϭ 15.014(11) Å , b ϭ 13.696(10) Å , c ϭ 19.890(15) Å , β ϭ 105.407(12)°, V ϭ 3943(5) Å 3 , Z ϭ 2). The structure consists of a packing of sandwich-like dimeric ion pairs in which two ozonide anions are interspersed between two tetrabutylammonium cations. Ammonia molecules from the solvent are

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Optische Absorptions-Spektroskopie an ionischen Ozoniden

Cited by 5 publications

References 16 publications

The nature of the chalcogen colour centres in ultramarine-type solids

The nature of the chalcogen colour centres in ultramarine-type solids

Ionic Ozonides

Dimeric Sandwich‐like Ion Pairs in the Crystal Structure of Tetrabutylammonium Ozonide Ammoniate

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