New Lanthanide-Containing Polytungstates Derived from the Cyclic P₈W₄₈Anion:  {Ln₄(H₂O)₂₈[K⊂P₈W₄₈O₁₈₄(H₄W₄O₁₂)₂Ln₂(H₂O)₁₀]^13-}_x, Ln = La, Ce, Pr, Nd

Abstract

The reaction of K28Li5H7[P8W48O184].92H2O with early lanthanides under hydrothermal and conventional conditions yields novel structures of the molecular formula Ln4(H2O)28K6Li7[K subsetP8W48O184(H4W4O12)2Ln2(H2O)10] congruent with 57H2O, Ln = La (1), Ce (2, 2a), Pr (3), Nd (4), in which the central cavity of the precursor anion is occupied by lanthanide cations and H4W4O12 moieties. The new heteropolyanions were characterized by elemental analysis, infrared spectroscopy, 31P NMR, and X-ray crystallography. All of the crystals are monoclinic, space group C2/m, with lattice constants (A, Epsilon) a = 33.061(3), b = 30.986(3), c = 15.1649(13), beta = 103.607(2), (1); a = 33.0577(16), b = 31.0562(15), c = 15.2320(7), beta = 104.015(2), (2); a = 33.0577(16), b = 31.0562(15), c = 15.2320(7), beta = 104.015(2), (2a); a = 33.007(2), b = 31.060(2), c = 15.2129(10), beta = 104.0140(10), (3); a = 32.913(19), b = 31.155(18), c = 15.135(9), beta = 103.495(11), (4); and Z = 2.

Nucleation Process in the Cavity of a 48‐Tungstophosphate Wheel Resulting in a 16‐Metal‐Centre Iron Oxide Nanocluster

“…Polyanion 1 contains-in the form of a cyclic arrangement-the unprecedented {Fe 16 (OH) 28 A C H T U N G T R E N N U N G (H 2 O) 4 } 20 + nanocluster, with 16 edge-and corner-sharing FeO 6 octahedra, grafted on the inner surface of the crown-shaped [H 7 P 8 III ions with the P 8 W 48 anion in aqueous, acidic medium (pH % 4), which can be regarded as an assembly process under confined geometries. One fascinating aspect is the possibility to model the uptake and release of iron in ferritin.…”

“…13À } x (Ln = La, Ce, Pr, Nd), [6] and Kortz and co-workers isolated the first transition-metal derivative, the 20-copper(II)-containing [Cu 20 Cl(OH) 24 A C H T U N G T R E N N U N G (H 2 O) 12 …”

Heterogeneous Wheel‐Shaped Cu20‐Polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25− Catalyst for Solvent‐Free Aerobic Oxidation of n‐Hexadecane

“…[20,22] In addition to Cu 20 , some of us have also synthesized iron-A C H T U N G T R E N N U N G (III), cobalt(II), organoruthenium(II), lanthanide (La, Ce, Pr, Nd) and uranyl containing derivatives of {P 8 W 48 }. [23][24][25][26] Here we report on a heterogeneous catalyst system composed of Cu 20 supported on 3-aminopropyltriethoxysilane (apts)-modified SBA-15 for solvent-free aerobic oxidation of n-hexadecane. The heterogeneous Cu 20 catalyst exhibits an exceptionally high turnover frequency (TOF) of 20 000 h À1 and is resistant to poisoning by CS 2 .…”

Actinide Polyoxometalates: Incorporation of Uranyl–Peroxo in U‐Shaped 36‐Tungsto‐8‐Phosphate

“…13À } x (Ln = La, Ce, Pr, Nd), [18] and our group reported the first transitionmetal and organoruthenium derivatives, [Cu 20 Cl(OH) 24 -…”