Issue 37, 2012

The self-assembly mechanism of the Lindqvist anion [W6O19]2− in aqueous solution: a density functional theory study

Abstract

The formation mechanism is always a fundamental and confused issue for polyoxometalate chemistry. Two formation mechanisms (M1 and M2) of the Lindqvist anion [W6O19]2− have been adopted to investigate it's self-assembly reaction pathways at a density functional theory (DFT) level. The potential energy surfaces reveal that both the mechanisms are thermodynamically favorable and overall barrierless at room temperature, but M2 is slightly dominant to M1. The formation of the pentanuclear species [W5O16]2− and [W5O15(OH)] are recognized as the rate-determining steps in the whole assembly polymerization processes. These two steps involve the highest energy barriers with 30.48 kcal mol−1 and 28.90 kcal mol−1, respectively, for M1 and M2. [W4O13]2− and [W4O12(OH)] are proved to be the most stable building blocks. In addition, DFT results reveal that the formation of [W3O10]2− experiences a lower barrier along the chain channel.

Graphical abstract: The self-assembly mechanism of the Lindqvist anion [W6O19]2− in aqueous solution: a density functional theory study

Supplementary files

Article information

Article type
Paper
Submitted
31 May 2012
Accepted
18 Jul 2012
First published
18 Jul 2012

Dalton Trans., 2012,41, 11361-11368

The self-assembly mechanism of the Lindqvist anion [W6O19]2− in aqueous solution: a density functional theory study

Z. Lang, W. Guan, L. Yan, S. Wen, Z. Su and L. Hao, Dalton Trans., 2012, 41, 11361 DOI: 10.1039/C2DT31166F

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