title: 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 [W(6)O(19)](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 [W(5)O(16)](2-) and [W(5)O(15)(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. [W(4)O(13)](2-) and [W(4)O(12)(OH)](-) are proved to be the most stable building blocks. In addition, DFT results reveal that the formation of [W(3)O(10)](2-) experiences a lower barrier along the chain channel.
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China.
authors.forename: Zhong-Ling
authors.initials: ZL
authors.lastname: Lang
authors.forename: Wei
authors.initials: W
authors.lastname: Guan
authors.forename: Li-Kai
authors.initials: LK
authors.lastname: Yan
authors.forename: Shi-Zheng
authors.initials: SZ
authors.lastname: Wen
authors.forename: Zhong-Min
authors.initials: ZM
authors.lastname: Su
authors.forename: Li-Zhu
authors.initials: LZ
authors.lastname: Hao
mesh_terms: D000838:Anions; D008958:Models, Molecular; D011789:Quantum Theory; D012996:Solutions; D017973:Tungsten Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000838:Anions; D012996:Solutions; D017973:Tungsten Compounds; D014867:Water