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Issue 29, 2012
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Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

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Abstract

The self-assembly of soluble molybdenum blue species from simple molybdate solutions has primarily been associated with giant mixed-valent wheel-shaped cluster anions, derived from the {MoV/VI154/176} archetypes, and a {MoV/VI368} lemon-shaped cluster. The combined use of Raman spectroscopy and kinetic precipitation as self-assembly monitoring techniques and single-crystal X-ray diffraction is key to mapping the realm of molybdenum blue species by establishing spherical {MoV/VI102}-type Keplerates as an important giant molybdenum blue-type species. We additionally rationalize the empirical effect of reducing agent concentration on the formation of all three relevant skeletal types: wheel, lemon and spheres. Whereas both wheels and the lemon-shaped {MoV/VI368} cluster are obtained from weakly reduced molybdenum blue solutions, considerably higher reduced solutions lead to {MoV/VI102}-type Keplerates.

Graphical abstract: Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

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Publication details

The article was received on 22 Mar 2012, accepted on 17 May 2012 and first published on 18 May 2012


Article type: Paper
DOI: 10.1039/C2DT30661A
Citation: Dalton Trans., 2012,41, 8951-8959
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    Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

    B. Botar, A. Ellern and P. Kögerler, Dalton Trans., 2012, 41, 8951
    DOI: 10.1039/C2DT30661A

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