Rates of ligand exchange between >FeIII-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution

Variable-temperature 17O NMR experiments were conducted on the nanometer-sized Keplerate Mo72Fe30 cluster, with the stoichiometry [Mo72Fe30O252(CH3COO)12[Mo2O7(H2O)]2[H2Mo2O8(H2O)](H2O)91]. approximately 150H2O. This molecule contains on its surface 30 Fe(H2O) groups forming a well-defined icosidodecahedron, and we estimated the rates of exchange of the isolated >FeIII-OH2 waters with bulk aqueous solution. Both longitudinal and transverse 17O-relaxation times were measured, as well as chemical shifts, and these parameters were then fit to the Swift-Connick equations in order to obtain the rate parameters. Correspondingly, we estimate: k(ex)298 = 6.7(+/-0.8) x 106 s-1, which is about a factor of approximately 4 x 104 times larger than the corresponding rate coefficient for the Fe(OH2)63+ ion of k(ex)298 = 1.6 x 102 s-1 (Grant and Jordan, 1981; Inorg. Chem. 20, 55-60) and DeltaH and DeltaS are 26.3 +/- 0.6 kJ mol-1 and -26 +/- 0.9 J mol-1 K-1, respectively. High-pressure 17O NMR experiments were also conducted, but the cluster decomposed slightly under pressure, which precluded confident quantitative estimation of the DeltaV. However, the increase in the reduced transverse-relaxation time with pressure suggests a dissociative character, such as a D or Id mechanism. The enhanced reactivity of waters on the Mo72Fe30 cluster is associated with an increase in the FeIII-OH2 bond length in the solid state of approximately 0.1 A relative to the Fe(OH2)63+ ion, suggesting that a correlation exists between the FeIII-OH2 bond length and k(ex)298. Although there are only few high-spin Fe(III) complexes where both exchange rates and structural data are available, these few seem to support a general correlation.     

Coverage dependent structures of oligopyridine adlayers on (111) oriented Ag films

The coverage dependent formation of ordered structures in vapor deposited 2,4'-bis(terpyridine)derivatives (2,4'-BTP) on (111) oriented Ag films was investigated by STM. Following a two-dimensional (2D) disordered gas phase at lowest coverages, a sequence of at least three ordered structures is observed with increasing coverage. These include a 'parallel chain structure' (PCS), a 'quasi-quadratic network' (QQN) structure, and a 'packed windmill structure' (PWS), with ideal coverages of 0.37, 0.4, and 0.44 molecules nm(-2). At intermediate coverages between 0.37 and 0.44 molecules nm(-2), these structures coexist in larger islands. The energetics of the different phases, whose structures are mainly determined by attractive C-H[dot dot dot]N bridges, are discussed in a picture including C-H[dot dot dot]N and C-H[dot dot dot]H-C interactions and lateral variations in the substrate-adsorbate interactions.     

Topologisch und elektronisch bemerkenswerte „reduzierte”︁ Cluster des Typs [V18O42(X)]n− (X = SO4, VO4) mit Td-Symmetrie und davon abgeleitete Cluster [V(18–p)As2pO42(X)]m− (X = SO3, SO4, H2O; p = 3, 4)

Reduced Clusters with Remarkable Topological and Electronic Properties of the Type of [V₁₈O₄₂(X)]^n? (X = SO₄, VO₄) with T_d-Symmetry and Related Clusters [V_(18—p)As_2pO₄₂(X)]^m? (X = SO₃, SO₄, H₂O; p = 3, 4) The novel cluster-compounds Na₆[V₁₈O₄₂H₉(VO₄)] · 21 H₂O, (NH₄)₈[V₁₈O₄₂(SO₄)] · 25 H₂O, K₆[V₁₅As₆O₄₂(H₂O)] · 8 H₂O, (NH₄)₆[V₁₄As₈O₄₂(SO₃)], (NH₄)₆[V₁₄As₈O₄₂(SO₄)] and [N(CH3)₃]₄[₄V₁₄As₈0₄₂(H₂0)] were prepared and characterized by IR- and UV/Vis/NIR-spectroscopy, magnetic measurements and complete crystal structure analysis. For structural data see Inhaltsübersicht. Topological relations to the rhombicuboctahedron spanned by 24 0-atoms of the genuine hypothetical a-Keggin ion, at which the square planes are capped by V?O or As₂O groups, are discussed. Of particular interest are the ?extended”? Keggin ions [V₁₈O₄₂(X)]ⁿ- (X = SO₄ VO₄), (formaly derived from the hypothetical genuine a-Keggin ion by addition of six V?O groups) which have quite different electron populations in spite of the same structure of their cluster shells.