title: Synthesis and structure of an "iron-doped" copper selenide cluster molecule: [Cu30Fe2Se6(SePh)24(dppm)4].
abstract: CuCl and bis(diphenylphosphanyl)methane (dppm) react in the presence of small amounts of FeCl(3) with PhSeSiMe(3) and Se(SiMe(3))(2) to yield [Cu(30)Fe(2)Se(6)(SePh)(24)(dppm)(4)]. The crystal structure of the compound was determined by single-crystal X-ray analysis to give a mixed copper selenide/selenolate cluster molecule of a new structural type incorporating two central iron atoms. The formal oxidation state of the iron atoms was determined by Mössbauer spectroscopy to be +3, in agreement with quantum chemical calculations and modeling of the magnetic data. In addition, Mössbauer studies show no magnetic hyperfine structure in zero field, and the magnetically perturbed spectrum displays a pattern typical for a diamagnetic species in a transverse field, suggesting a singlet ground state. However, the inclusion of the iron atoms has a distinct influence on the optical properties of the compound compared to similar clusters containing only copper and selenium atoms.
authors.affiliation: Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany. eichhoefer@int.fzk.de
authors.forename: Andreas
authors.initials: A
authors.lastname: Eichhöfer
authors.forename: Jolanta
authors.initials: J
authors.lastname: Olkowska-Oetzel
authors.forename: Dieter
authors.initials: D
authors.lastname: Fenske
authors.forename: Karin
authors.initials: K
authors.lastname: Fink
authors.forename: Valeriu
authors.initials: V
authors.lastname: Mereacre
authors.forename: Annie K
authors.initials: AK
authors.lastname: Powell
authors.forename: Gernot
authors.initials: G
authors.lastname: Buth