Reactivity of chalcogenostannate compounds:: Syntheses, crystal structures, and electronic properties of novel compounds containing discrete ternary anions [M4II(μ4-Se)(SnSe4)4]10- (MII = Zn, Mn)

被引:107
作者
Dehnen, S [1 ]
Brandmayer, MK [1 ]
机构
[1] Univ Karlsruhe, Inst Anorgan Chem, D-76128 Karlsruhe, Germany
关键词
D O I
10.1021/ja029601b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reactions of K4[SnSe4]·1.5MeOH with ZnCl2 or MnCl2·4H2O in water/methanol mixtures yield novel compounds [K10(H2O)16(MeOH)0.5][M4(μ4-Se)(SnSe4)4] (M = Zn, 2; Mn, 3) in high yields; 2 and 3 contain the first discrete ternary Zn/Sn/Se or Mn/Sn/Se cluster anions. Both compounds were unambiguously characterized by X-ray diffraction (tetragonal, space groups P43212 and P41212, respectively) revealing chiral anionic structures within chiral crystals. Optical spectra of 2 and 3 indicate energy differences for the lowest electronic excitations (Eg = 2.57 eV, 2; 2.27 eV, 3) that are very close to the band gap values observed for mesoporous solids with polymeric M/Sn/E networks. DFT investigations on the electronic situation and first ESR studies agree in that they demonstrate a high-spin ground state in the case of 3 with 20 unpaired electrons at four uncoupled MnII centers. Copyright © 2003 American Chemical Society.
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页码:6618 / 6619
页数:2
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  • [31] ZIMMERMANN C, 2000, ANGEW CHEM INT EDIT, V41, P4269