Ortho-chalcogenostannates as ligands:: Syntheses, crystal structures, electronic properties, and magnetism of novel compounds containing ternary anionic substructures [M4(μ4-Se)(SnSe4)4]10- (M = Mn, Zn, Cd, Hg), ∞3[Hg4(μ4Se)(SnSe4)3]6-}, or ∞1{[HgSnSe4]2-}

By reaction of K-4[SnSe4].1.5-MeOH with CdCl2 or Hg(OAc)(2) in water/methanol it was possible to prepare single crystals of four novel compounds that contain ternary anionic coordination oligomers and polymers: [K-10(H2O)(16)(MeOH)(0.5)][M-4(mu(4)-Se)(SnSe4)(4)] (4: M=Cd, 5: M=Hg), [K-6(H2O)(3)][Hg-4(mu(4)-Se)(SnSe4)(3)].MeOH (6), and K-2[HgSnSe4] (7), which were structurally characterized by single crystal X-ray diffraction. The optical absorption properties of the isostructural compounds 4 and 5, as well as those of the recently reported Zn (2) and Mn (3) analogues, were studied by UV-visible spectroscopy. These investigations showed the quaternary phases to have relatively small optical gaps for their molecular size (2.2-2.6 eV), which are similar to the excitation energies that were observed for mesostructured solids of the respective combination of elements. According to DFT investigations on the ternary anions, an experimentally observed difference between the absorption behavior of the d(10) compounds 2, 4, and 5 and the open-shell d(5) compound 3 is in line with different characters of the frontier orbitals in the two cases. Both the calculations and a magnetic measurement on 3 demonstrated antiferromagnetic coupling between the mu(4)-Se-bridged Mn centers.