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