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Synthesis, Characterization, and Surface Tethering of Sulfide-Functionalized Ti₁₆-oxo-alkoxy Cages

Eslava, Salvador; Papageorgiou, Anthoula C.; Beaumont, Simon K.; Kyriakou, Georgios; Wright, Dominic S.; Lambert, Richard M.


Salvador Eslava

Anthoula C. Papageorgiou

Georgios Kyriakou

Dominic S. Wright

Richard M. Lambert


The parent cage [Ti16O16(OEt)32] readily undergoes ligand exchange with a range of primary alcohols to yield species of the type [Ti16O16(OEt)32−x(OR′)x], with R′ = Me, n-Pr, and n-Bu with x of up to 8. Attempted ligand exchange using the thiol [HO(CH2)4SH] in an attempt to produce functionalized cages suitable for tethering to Au surfaces failed, resulting only in the polymerization of the Ti oxo-cores. However, the use of the thioether [HO(CH2)4SCH3] resulted in successful thio-functionalization and preservation of the Ti16 cage core, likely due to methyl protection on the sulfide which precludes further intermolecular reaction with other cage molecules. ESI-MS and NMR showed that the resulting substituted cage [Ti16O16(OEt)24{O(CH2)4SCH3}8] contained eight methylthio-n-butoxy ligands in two groups of four pseudoequivalent positions. High resolution XPS and STM demonstrated that this sulfide-functionalized cage underwent covalent tethering to Au surfaces involving five sulfur linkages per cage, forming a monolayer of adsorbed species in which the molecular integrity had been preserved. In contrast, the parent oxo-alkoxy cage underwent extensive decomposition, rendering it useless as a building block for specific surface architectures.


Eslava, S., Papageorgiou, A. C., Beaumont, S. K., Kyriakou, G., Wright, D. S., & Lambert, R. M. (2010). Synthesis, Characterization, and Surface Tethering of Sulfide-Functionalized Ti₁₆-oxo-alkoxy Cages. Chemistry of Materials, 22(18), 5174-5178.

Journal Article Type Article
Online Publication Date Aug 17, 2010
Publication Date Sep 28, 2010
Deposit Date Mar 8, 2014
Journal Chemistry of Materials
Print ISSN 0897-4756
Electronic ISSN 1520-5002
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 22
Issue 18
Pages 5174-5178