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Chapter 3 Published Results = 21.629(2) Å, b = 26.869(3) Å, c = 31.611(3) Å, α = 80.463(3)°, β = 72.936(4)°, γ = 75.999(4)°, V = 16951.2 Å 3 and Z = 2. c) The praseodymium derivative of the {Ln 2 W 28 } family crystallizes in the triclinic system, space group P-1, with a = 21.110(8) Å, b = 26.903(8) Å, c = 31.154(10) Å, α = 81.125(11)°, β = 73.771(13)°, γ = 76.903(12)°, V = 16467.77 Å 3 and Z = 2. d) The neodymium derivative of the {Ln 2 W 28 } family crystallizes in the triclinic system, space group P-1, with a = 14.837(3) Å, b = 21.803(4) Å, c = 23.596(4) Å, α = 88.899(7)°, β = 86.092(6)°, γ = 75.540(7)°, V = 7374.23 Å 3 and Z = 2. e) The gadolinium derivative of the {Ln 2 W 28 } family crystallizes in the triclinic system, space group P-1, with a = 14.8426(19) Å, b = 21.779(3) Å, c = 23.581(3) Å, α = 89.059(4)°, β = 86.325(4)°, γ = 75.426(4)°, V = 7362.12 Å 3 and Z = 2. [14] a) T. Lehmann, J. Fuchs, Z. Naturforsch. B 1988, 43, 89; b) H. Hartl, R. Palm, J. Fuchs, Angew. Chem. 1993, 105, 1545; Angew. Chem. Int. Ed. Engl. 1993, 32, 1492. [15] a) D-L. Long, H. Abbas, P. Kögerler, L. Cronin, J. Am. Chem. Soc. 2004, 126, 13880; b) H. N. Miras, J. Yan, D.-L. Long, L. Cronin, Angew. Chem. Int. Ed. 2008, 47, 8420. [16] D. Altermatt, I. D. Brown, Acta. Cryst. 1985, B41, 244. 95
Chapter 3 Published Results 3.B. Lanthanide‐Containing Heteropolytungstates: 3.B.1. Mono‐ and Di‐Lanthanide Derivatives of Tungstoarsenates(III) A. H. Ismail, B. S. Bassil, I. Römer, N. C. Redeker, U. Kortz, Z. Naturforsch. B, 2010, 65b, 383 3.B.1.1. Introduction Polyoxometalates (POMs) are a diverse class of anionic metal-oxygen cage complexes formed predominantly of early transition metals (groups V and VI) in high oxidation states. The large compositional and structural versatility of POMs gives rise to various applications in fields such as catalysis, medicine, analytical chemistry, and material science. 1 Although the first polyanion has been made already in 1826, the mechanism of POM formation is still not well understood and usually described as self-assembly. 1 POMs are usually formed via condensation of mononuclear metalate ions in acidified aqueous solutions. In particular, polyoxotungstates are effective homogeneous photocatalysts useful for the degradation of organic pollutants. 2 Lanthanide-containing POMs are in general less investigated than their 3d-transitionmetal analogues, but recently there have been more reports on the former class. 3 POMscontaining lanthanides show interesting properties in areas such as photoluminescence, catalysis, electrochemistry, and magnetism. 4,5 Due to their larger sizes and subsequently larger coordination numbers compared to 3d transition metal ions, lanthanide ions exhibit a different coordination mode to lacunary POM precursors resulting in novel and sometimes unexpected structures. 6 Lacunary POM precursors containing a hetero group with a lone pair of electrons (e. g. As III , Sb III ) are of particular interest, because the lone pair does not allow the closed Keggin unit to form, resulting in a very different reactivity as compared to lacunary POMs with a 96
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