Single-Micelle and Single-Zinc-Particle Imaging Provides Insights into the Physical Processes Underpinning Organozinc Reactions in Water.

Abstract

Micelles on the surfaces of individual metallic zinc particles are imaged by fluorescence microscopy with sensitivity up to single micelles. These micelles are made fluorescent to enable imaging, through the incorporation of boron dipyrromethene fluorophores as representative organic molecular "cargo". Highlighting an advantage of this in situ and sensitive fluorescence technique, the same micelles are not visible by ex situ scanning electron microscopy/energy dispersive X-ray spectroscopy analysis. Examination of micellar solutions with zinc reveals an aging process: micelles do not immediately adhere to the zinc surfaces upon mixing but rather build up over time. Furthermore, at longer times, smaller zinc particles become fully encased in micelle "shells". Once adhered, micelles remain in the local regions of the zinc surface for the duration of the imaging experiments (>2 h). Single micelles are imaged in solution, and their molecular contents are characterized. Two-color fluorescence crossover experiments show that micelles adhered to the surface of the zinc exchange molecular contents with micelles in solution, achieving molecular exchange equilibrium in ∼2.5 h. Unique (non-ensemble averaged) exchange kinetics are displayed by micelles at different locations on the zinc surface, consistent with exchange kinetics of single micelles or small local clusters of micelles. The aging of the micellar solutions and the rate of exchange while on the surface of the zinc suggest that micelle mass transport processes may contribute to overall reaction barriers in sustainable organozinc cross-coupling reactions in micellar water. The observed aging of the system suggests routes for improvement of preparative, bench-scale synthetic reactions involving micellar preparations of organozinc compounds.