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Lookup NU author(s): Dr Ulrich Baisch
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Novel synthetic approaches to rare earth nitrido- and oxonitridocarbonates are described. Dioxy mono-carbodiimides (Ln(2)O(2)CN(2)) from the second half of the lanthanide series are accessible by insertion of supercritical CO2 into lanthanide amido compounds (e.g. [(Cp2ErNH2)(2)]), forming single-source precursors. Ammonolyses of amorphous carbamate compounds afford phase pure Ln(2)O(2)CN(2), which are also accessible via the crystalline carbamate compound [Ln(7) {mu-eta(1):eta(2)-OC(OtBu)NH}Cp-4] (Ln = Y, Ho, Er, Yb). Urea complexes and homo-leptic cyanates of europium and strontium were synthesized by solid-state reaction of urea with the respective metals. Subsequent thermal treatment (160-240 degrees C) results in formation of solvent-free homoleptic cyanates. The Eu2+-doped compounds [Sr(OCN)(2)(urea)]:Eu2+ andSr(OCN)(2):Eu2+ as well as the respective pure europium compounds exhibit strong broad band emissions due to 4f(6)5d(1)-4f(7) transitions in the bluish green region. Furthermore, rare earth dicyanamides Ln[N(CN)(2)](3)center dot 2H(2)O as well as Ln[N(CN)(2)](3) (with Ln = Eu, Tb, and Gd) were prepared by ion exchange in aqueous solution, followed by evaporation of the solvent at room temperature. Condensed nitridocarbonates such as rare earth tricyanomelaminates [NH4]Ln[HC6N9](2)[H2O](7)center dot H2O (La = La Nd, Sm-Dy) were obtained through ion exchange reactions. The luminescence properties of the europium and terbium dicyanamides as well as the tricyanomelaminates have been explored in detail.
Author(s): Pagano S, Zeuner M, Baisch U, Schnick W
Publication type: Article
Publication status: Published
Journal: Zeitschrift fuer Anorganische und Allgemeine Chemie
Year: 2010
Volume: 636
Issue: 12
Pages: 2212-2221
Print publication date: 22/06/2010
ISSN (print): 0044-2313
ISSN (electronic): 1521-3749
Publisher: Wiley - VCH Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/zaac.201000159
DOI: 10.1002/zaac.201000159
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