Effects of organic ammonium cations on the isolation of {Ti4} cyclic clusters from water: An17O NMR study

Weiming Liu, Caiyun Liu, Wenli Wu, Guanyun Zhang, Jian Zhang, Chen Ho Tung, Yifeng Wang

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


For the preparation of aqueous Ti-oxo clusters (TOCs) without organic ligands, organic ammonium cations (OACs) are important, but the mechanism is obscure. Here, the Ti4+/SO42-system was chosen as a model to investigate the roles of OACs. Three {Ti4} clusters were isolated from this system with different cationic additives. Structural analysis revealed a structural role of OACs: the hierarchically ordered array of the OACs in the organic layers was responsible for the stability and formation of crystalline precipitates.17O NMR spectroscopy was used to study the interactions of OACs and SO42-with the Ti-oxo species in water under highly acidic conditions. SO42-enhanced the condensation of Ti4+by binding to the TOC species. OACs could not enhance the condensation of Ti4+but could change the solution speciation and especially promote the formation of {Ti18O27} clusters. We speculate that OACs interact with the cationic/neutral TOCs through anionic bridges to change the speciation. Under the synthetic conditions of {Ti4}, {Ti18O27} is the native TOC in solutions but {Ti4} is not.

Original languageEnglish
Pages (from-to)5957-5964
Number of pages8
JournalDalton Transactions
Issue number18
StatePublished - 14 May 2020
Externally publishedYes

ASJC Scopus subject areas

  • Inorganic Chemistry


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