TY - JOUR
T1 - Flux synthesis of the noncentrosymmetric cluster compounds Cs2SnAs2Q9 (Q = S, Se) containing two different polychalcoarsenite β-[AsQ4]3- and [AsQ5]3- ligands
AU - Iyer, Ratnasabapathy G.
AU - Do, Junghwan
AU - Kanatzidis, Mercouri G.
PY - 2003/3/10
Y1 - 2003/3/10
N2 - 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.
AB - 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.
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U2 - 10.1021/ic0260771
DO - 10.1021/ic0260771
M3 - Article
C2 - 12611513
AN - SCOPUS:0037430179
SN - 0020-1669
VL - 42
SP - 1475
EP - 1482
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -