Redox-Switched Amphiphiles: Oxidized Ferrocene Derivatives Form Stable Vesicles When Either One or Two Alkyl Tails Are Present

Abstract

Thirty ferrocene derivatives were prepared and their ability to form vesicles in aqueous solution when oxidized was assessed. The compounds included alkyl ferrocenylmethyl ether derivatives of the form C 10 H 9 FeCH 2 OR in which R = octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosanyl. One single-tailed amine derivative, C 10 H 9 FeCH 2 NR 2 , R = octadecyl, was studied. Alkylferrocene derivatives had the form C 10 H 9 FeR in which R = butyl, decyl, tetradecyl, hexadecyl, octadecyl, eicosanyl and docosanyl. Sixteen symmetrical 1,1Ј-disubstituted ferrocenes were also studied. Three ethers were of the form C 10 H 8 Fe-1,1Ј-(CH 2 OR), 2 , R = tetradecyl, hexadecyl and octadecyl. Four corresponding dialkyl derivatives of the form C 10 H 8 Fe-1,1Ј-R 2 , R = decyl, tetradecyl, hexadecyl and octadecyl, were assessed. Finally, a range of 1,1Ј-disubstituted ferrocene derivatives were analyzed. These all had the form C 10 H 8 Fe-1,1Ј-(COR) 2 , for which R has the following identities: octyl, tridecyl, pentadecyl and heptadecyl (ketones); heptadecyloxy, 3-cholesteryl and 3-cholestanyl (esters); and two amides, R = NHC 18 H 37 and N(C 18 H 37 ) 2 . The alkyl and ether derivatives could be readily oxidized and formed vesicular aggregates upon sonication. The ketones, esters and amides could be oxidized but the ferricenium derivatives did not form stable aggregates. An interesting observation is that the aggregates formed were vesicular whether the ferrocene derivative had one or two alkyl tails.

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

“…The disubstituted derivatives were prepared by adding the ferrocene solution to the acid chloride-AlCl3 complex, using a molar ratio of both the acid chloride and the aluminum chloride to ferrocene of 4:3. The synthesis followed a literature procedure by Wang and Gokel [13], reagents being scaled up at least 10 times, with other minor modifications. Acylferrocenes and 1,1′-diacylferrocenes were prepared by Friedel-Crafts acylation and converted to the alkyl counterparts by the Clemmensen reduction.…”

“…and Gokel [13]. Neutral ferrocene is yellow in solution while the positively charged ferrocenium is blue [15].…”

“…aromatic substitution [13] and [14], like benzene, to allow the incorporation of long alkyl chains and it contains iron and thus the surfactant is both organic and inorganic. One of the simplest and most characteristic reactions of metallocenes is their oxidation to cationic species involving loss of an electron; ferrocene can be oxidized to the corresponding ferrocenium cation electrolytically, photolytically and by a wide variety of organic and inorganic oxidizing agents.…”

“…One of the simplest and most characteristic reactions of metallocenes is their oxidation to cationic species involving loss of an electron; ferrocene can be oxidized to the corresponding ferrocenium cation electrolytically, photolytically and by a wide variety of organic and inorganic oxidizing agents. When oxidized, a blue, relatively stable ferrocenium cation is formed [13]. The corresponding alkylferrocenium salts can then be used to modify clay to obtain a new organically modified clay which can then be used for nanocomposite formation.…”

Synthesis and thermal analysis of some ferrocene derivatives

“…Organometallics combine the properties of transition metal elements into organic frame works providing access to a range of properties and geometries which are denied to other organic compounds [1][2][3][4][5]. For designing new organometallic materials which display thermotropic liquid crystalline behavior, the thermal stability of a newly synthesized compound is an important feature which affects its practical applications, especially in fields where high temperature processing or operation is required.…”