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

被引：34

作者：

Botar, Bogdan ^{[1
]}

Ellern, Arkady ^{[2
]}

Koegerler, Paul ^{[1
,3
]}

机构：

[1] Forschungszentrum Julich, Peter Grunberg Inst PGI 6, D-52425 Julich, Germany

[2] Iowa State Univ, Ames Lab, Ames, IA 50011 USA

[3] Rhein Westfal TH Aachen, Inst Anorgan Chem, D-52074 Aachen, Germany

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 29期

关键词：

BUILDING-BLOCKS; METAL-OXIDE; KEPLERATE; NANOCHEMISTRY; DISCRETE; MYSTERY; SPHERES; WHEELS; ATOMS; H2O;

D O I：

10.1039/c2dt30661a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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 {Mo-154/176(V/VI)} archetypes, and a {Mo-368(V/VI)} 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 {Mo-102(V/VI)}-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 {Mo-368(V/VI)} cluster are obtained from weakly reduced molybdenum blue solutions, considerably higher reduced solutions lead to {Mo-102(V/VI)}-type Keplerates.

引用

页码：8951 / 8959

页数：9

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