Preparation, size control, surface deposition, and catalytic reactivity of hydrophobic corrolazine nanoparticles in an aqueous environment.

Nanoparticles, each consisting of one of the three molecular corrolazine (Cz) compounds, H(3)(TBP(8)Cz), Mn(III)(TBP(8)Cz), and Fe(III)(TBP(8)Cz) (TBP(8)Cz = octakis(4-tert-butylphenyl)corrolazinato), were prepared via a facile mixed-solvent technique. The corrolazine nanoparticles (MCz-NPs) were formed in H(2)O/THF (10:1) in the presence of a small amount of a polyethylene glycol derivative (TEG-ME) added as a stabilizer. This technique allows highly hydrophobic Czs to be "dissolved" in an aqueous environment as nanoparticles, which remain in solution for several months without visible precipitation. The MCz-NPs were characterized by UV-visible spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM) imaging, and shown to be spherical particles from 100-600 nm in diameter with low polydispersity indices (PDI = 0.003-0.261). Particle size is strongly dependent on Cz concentration. The H(3)Cz-NPs were adsorbed on to a modified self-assembled monolayer (SAM) surface and imaged by atomic force microscopy (AFM). Adsorption resulted in disassembly of the larger H(3)Cz-NPs to smaller H(3)Cz-NPs, whereby the resulting particle size can be controlled by the surface energy of the monolayer. The Fe(III)Cz-NPs were shown to be competent catalysts for the oxidation of cyclohexene with either PFIB or H(2)O(2) as external oxidant. The reactivity and product selectivity seen for Fe(III)Cz-NPs differs dramatically from that seen for the molecular species in organic solvents, suggesting that both the nanoparticle structure and the aqueous conditions may contribute to significant changes in the mechanism of action of the Fe(III)Cz catalyst.