Iron-Carbonyl Aqueous Vesicles (MCsomes) by Hydration of [Fe(CO){CO(CH2)5CH3}(Cp)(PPh3)] (FpC6): Highly Integrated Colloids with Aggregation-Induced Self-Enhanced IR Absorption (AI-SEIRA).

Abstract

Self-assembly of hydrophobic molecules into aqueous colloids contradicts common chemical intuition, but has been achieved through hydration of [Fe(CO){CO(CH2)5CH3}(Cp)(PPh3)] (FpC6). FpC6 has no surface activity, no NMR signals in D2O and no critical aggregation concentration (CAC) in H2O. The molecule, however, contains both acyl and terminal CO groups that are prone to being hydrated. By adding water to a solution in THF, self-assembly of FpC6 can be initiated through water-carbonyl interactions (WCIs) with the highly polarized acyl CO groups. This aggregation subsequently enhances the hydration of the acyl CO groups and also induces the WCI of otherwise unhydrated terminal CO groups. The resultant metal-carbonyl aggregates have been proved to be bilayer vesicles with iron complexes exposed towards water and alkyl chains forming inner walls (MCsomes). These MCsomes show high structure integration upon dilution due to the hydrophobic nature of the building blocks. The highly polarized CO groups on the surface of the MCsomes result in a negative zeta potential (-65 mV) and create a local electric field, which significantly enhances the IR absorption of CO groups by more than 100-fold. This is the first discovery of aggregation-induced self-enhanced IR absorption (AI-SRIRA) without the assistant of external dielectric substrates. Highly integrated MCsomes are, therefore, promising as a novel group of materials, for example, for IR-based sensing and imaging.