Synthesis, characterization, and surface tethering of sulfide- functionalized Ti-oxo-alkoxy cages

S Eslava, A.C. Papageorgiou, S.K. Beaumont, G. Kyriakou, D.S. Wright, R.M. Lambert

Research output: Contribution to journalArticlepeer-review

21 Citations (SciVal)


The parent cage [TiO(OEt)] readily undergoes ligand exchange with a range of primary alcohols to yield species of the type [TiO(OEt)(OR′) ], with R′ = Me, n-Pr, and n-Bu with x of up to 8. Attempted ligand exchange using the thiol [HO(CH)SH] 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(CH)SCH] resulted in successful thio-functionalization and preservation of the Ti 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 [TiO(OEt) {O(CH)SCH}] 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.
Original languageEnglish
Pages (from-to)5174-5178
Number of pages5
JournalChemistry of Materials
Issue number18
Publication statusPublished - 28 Sept 2010


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