Flux synthesis of the noncentrosymmetric cluster compounds Cs2SnAs2Q9 (Q = S, Se) containing two different polychalcoarsenite β-[AsQ4]3- and [AsQ5]3- ligands

Ratnasabapathy G. Iyer, Junghwan Do, Mercouri G. Kanatzidis

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Abstract

Two noncentrosymmetric quaternary tin chalcoarsenates, Cs2SnAs2S9 (1) and Cs2SnAs2Se9 (2), were synthesized by the polychalcoarsenate flux method. Compound 1 crystallizes in the orthorhombic space group Pmc21 with a = 7.386(3) Å, b = 14.614(5) Å, c = 14.417(5) Å, and Z = 4. Compound 2 crystallizes in the monoclinic space group P21 with a = 7.715(5) Å, b = 17.56(1) A, c = 7.663(5) Å, β = 115.86(1)°, and Z = 2. Both structures contain the same tin-centered molecular cluster anions {Sn[AsQ2(Q2)][AsQ(Q2)2]} 2- (Q = S, Se) separated by Cs cations. The Sn4+ ion is in a distorted octahedral environment coordinated by two different pyramidal-shaped tridentate ligands, [AsQ2(Q2)]3- and [AsQ(Q2)2]3-. These compounds absorb visible light at energies above 1.98 and 1.45 eV for 1 and 2, respectively. Differential thermal analysis revealed that 1 melts at 350 °C and on cooling gives a glass. The glass recrystallizes at 268 °C upon subsequent heating. Compound 2 melts at 258 °C.

Original languageEnglish
Pages (from-to)1475-1482
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number5
DOIs
Publication statusPublished - Mar 10 2003

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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