title: Iterative mass spectrometry and X-ray crystallography to study ion-trapping and rearrangements by a flexible cluster.
abstract: An important aspect of chemical reactions involves understanding the intermediate steps from reactants to products. The iterative use of mass spectrometry and X-Ray crystallography is demonstrated to be a powerful combination in this respect. We have applied them in identifying molecular clusters in solution followed by their solid-state structural characterizations. We used a key ligand, 2-[(2-hydroxy-3-methoxy-benzylidene)-amino]-ethanesulfonate (L), which serves as chelating/bridging units to stabilize the precursor [Li₄Ni₆(OH)₂(L)₆(CH₃CN)₆](ClO₄)₂·4CH₃CN. The results of subsequent reactions witness a cascade of processes involving fragmentation, inner bridging ligand substitution (OH⁻ to OCH₃⁻), changing modes of binding (chelate to monodentate) of the key ligand, ion-trapping and exchange (Li⁺, Na⁺ and Ca²⁺) and their site preferences, coordinating and non-coordinating solvents (CH₃CN to CH₃OH, H₂O and EtOH) replacement. The flexibility of the Ni₃OL₃ species in solution permits the formation of six derivatives. The complimentary techniques open a broader prospect for cluster design and applications.
authors.affiliation: 1] School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education) Guilin, 541004, P. R. China [2] Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, P. R. China.
authors.forename: Kun
authors.initials: K
authors.lastname: Zhang
authors.affiliation: Institut de Chimie de Strasbourg, CNRS-UMR 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France.
authors.forename: Mohamedally
authors.initials: M
authors.lastname: Kurmoo
authors.affiliation: School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education) Guilin, 541004, P. R. China.
authors.forename: Lian-Qiang
authors.initials: LQ
authors.lastname: Wei
authors.affiliation: 1] School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education) Guilin, 541004, P. R. China [2] Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, P. R. China.
authors.forename: Ming-Hua
authors.initials: MH
authors.lastname: Zeng