Copper(I) d10⋯d10 interactions and diselenide(1-) radical anions in mixed valent selenides Cu4- δBiSe4I

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

Abstract

Melting reactions of copper, CuI, selenium, and Bi2Se 3 yielded black, shiny needles of Cu4BiSe4I = Cu4BiSe2(Se2)I. The compound decomposes peritectically above 635(5) K and crystallizes in the orthorhombic space group Pnma with a = 960.1(1) pm, b = 413.16(3) pm, and c = 2274.7(2) pm (T = 293(2) K). In the crystal structure, strands ${1}\atop{{\infty}} $[BiSeSe2/2(Se2)2/2]3- run along [010]. Therein, the bismuth(III) cation is coordinated by five selenium atoms, which form a square pyramid. The copper(I) cations are coordinated tetrahedrally by selenide, diselenide and iodide ions. Edge-sharing of these tetrahedra results in zigzag chains of copper cations with short distances of 262.7(4) pm. Enhanced dispersion of the 3d bands, the Crystal Orbital Hamilton Populations (COHP), and disynaptic ELI-D basins indicate weakly attractive d10⋯d10 interactions between the copper cations. The semiconducting properties and the calculated electronic band structure suggest an electron-precise compound. In copper-deficient Cu 3.824(8)BiSe4I, the Cu⋯Cu distances are 5 pm shorter, and Raman spectroscopy indicates the presence of diselenide(1-) radical anions besides the diselenide(2-) groups. As a result, in Cu 3.824(8)BiSe4I, selenium coexists in the oxidations states -II, -I, and -0.5.

Details

OriginalspracheEnglisch
Seiten (von - bis)1131-1136
Seitenumfang6
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang637
Ausgabenummer9
PublikationsstatusVeröffentlicht - Juli 2011
Peer-Review-StatusJa

Externe IDs

ORCID /0000-0002-2391-6025/work/166325872

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth, Closed-shell interactions, Copper, Mixed-valent compounds, Radical anions