Nano islet formation of formyl- and carboxyferrocene, -ruthenocene, -osmocene and cobaltocenium on amine-functionalized silicon wafers highlighted by crystallographic, AFM and XPS studies

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• 作者：Monika Trzebiatowska-Gusowska ; Anna G?gor ; Elizabeth Coetsee ; Elizabeth Erasmus ; Hendrik C. Swart ; Jannie C. Swarts
• 关键词：Osmocene ; Cobaltocene ; Silicon wafers ; Amine surfaces ; XPS ; AFM
• 刊名：Journal of Organometallic Chemistry
• 出版年：2013
• 出版时间：15 November, 2013
• 年：2013
• 卷：745-746
• 期：Complete
• 页码：393-403
• 全文大小：1656 K

文摘

Surface-hydroxylated silicon wafers, 8, were reacted with 3-aminopropyltrimethoxysilane, 9, to create wafers with amine-functionalized surfaces, 10. The metallocenylaldehydes FcCHO, 1 (Fc?=?ferrocenyl?=?Fe^II(C₅H₅)(C₅H₄)), RcCHO, 2 (Rc?=?ruthenocenyl?=?Ru^II(C₅H₅)(C₅H₄)), and OcCHO, 3 (Oc?=?osmocenyl?=?Os^II(C₅H₅)(C₅H₄)) as well as the carboxylic acids FcCOOH, 4, RcCOOH, 5, OcCOOH, 6, and Cc⁺COOH¡¤PF₆^?, 7 (Cc⁺?=?cationic cobaltocenium?=?[Co^III(C₅H₅)(C₅H₄)]⁺), were reacted with 10 to covalently anchor the metallocenes on the wafers either via an imine (-CHN-) or amide (-NHCO-) bond. The aldehydes were anchored more effectively than the carboxylic acids. Binding energies of all important atoms in all seven systems were determined by XPS measurements. Metal binding energies of the amide-bonded metallocenes were consistently larger (up to 0.6?eV) than those of the imine-anchored systems. AFM and SEM measurements showed that the covalently anchored metallocenes aggregate into nano-islets of diameter between 40 and 100?nm depending on the metallocene and type of anchoring bond. Up to seven additional layers of unreacted metallocenylaldehyde or -acid further stacked on top of the main layer of metallocene to form each islet. These additional layers of metallocene of each islet are stabilized by a large network of secondary and/or tertiary bonding forces. The main film surfaces have average thicknesses ranging between 2 and 6?nm, while film roughness, which is mostly associated with the islets, was with one exception (that of the Oc-CONH- surface 14) between 17 % and 68 % of the film thickness. The crystal structures for OcCHO, 3, and Cc⁺COOH¡¤PF₆^?, 7, was determined and the observed tertiary and secondary intermolecular interactions between independent molecules explains the formation of the nano-islets of each metallocene when anchored onto the aminated silicon wafers.