Organometallic, Nonclassical Surfactant with Gemini Design Comprising π-Conjugated Constituents Ready for Modification.

Surfactants are functional molecules comprising a water-compatible head group and a hydrophobic tail. One of their features is the formation of self-assembled structures in contact with water, for instance, micelles, vesicles, or lyotropic liquid crystals. One way to increase the functionality of surfactants is to implement moieties containing transition-metal species. Ferrocene-based surfactants represent an excellent example because of the distinguished redox features. In most existing ferrocene-based amphiphiles, an alkyl chain is classically used as the hydrophobic tail. We report the synthesis and properties of 1-triisopropylsilylethynyl-1'-trimethylammoniummethylferrocene (FcNMeTIPS). In FcNMeTIPS, ferrocene is part of the head group (Gemini design) but is also attached to a (protected) π-conjugated ethynyl group. Although this architecture differs from that of classical amphiphiles and those of other ferrocene-based amphiphiles, the compound shows marked surfactant properties comparable to those of lipids, exhibiting a very low value of critical aggregation concentration in water (cac = 0.03 mM). It forms classical micelles only in a very narrow concentration range, which then convert into monolayer vesicles. Unlike classical surfactants, aggregates already form at a very low concentration, far beneath that required for the formation of a monolayer at the air-water interface. At even higher concentration, FcNMeTIPS forms lyotropic liquid crystals, not only in contact with water, but also in a variety of organic solvents. As an additional intriguing feature, FcNMeTIPS is amenable to a range of further modification reactions. The TIPS group is easily cleaved, and the resulting ethynyl function can be used to construct heterobimetallic platinum-ferrocene conjugates with -Pt(PEt)X (X = Cl, I) complex entities, leading to a heterobimetallic surfactant. We also found that the benzylic α-position of FcNMeTIPS is rather reactive and that the attached ammonium group can be exchanged by other substituents (e.g., -CN), which offers additional opportunities for further functionalization. Although FcNMeTIPS is reversibly oxidized in voltammetric and UV-vis spectroelectrochemical experiments, the high reactivity at the α-position is also responsible for the instability of the corresponding ferrocenium ion, leading to a polymerization reaction.