Diazirine-Modified Gold Nanoparticle: Template for Efficient Photoinduced Interfacial Carbene Insertion Reactions

Photolysis of a 3-aryl-3-(trifluoromethyl)diazirine-modified monolayer-protected gold nanoparticles (2-C(12)MPNs), with a core size of 1 8 +/- 0 3 nm, in the presence of model carbene trapping reagents leads to efficient, essentially quantitative, modification of the interface via carbene insertion reactions The utility of carbene insertion reactions as a general approach for the modification of Au-MPNs to provide a breadth of new structures available was demonstrated using acetic acid, methanol, benzyl alcohol, phenol, benzylamine, methyl acrylate, and styrene (10a-g, respectively) as electrophilic carbene trapping agents to form the corresponding modified 3a-g-C(12)MPNs The 1.8 +/- 0 3 mu gold nanoparticles bearing a diazirine group (2-C(12)MPNs) were synthesized using the humid exchange reaction with the requisite 3-aryl-3-(trifluoromethyl)diazirinealkylthiol The 2-C(12)MPNs and the resulting products of the reaction on the MPN (3a-g-C12MPN) were fully characterized by IR, H-1 NMR. and F-19 NMR spectroscopy and when applicable, transmission election microscopy (TEM) Verification for the 3a-g-C(12)MPNs was accomplished by comparison of the spectral data to those of obtained for the photoreactions of 3-(3-methoxyphenyl)-3-(trifluoromethyl)-3H-diazirine as a model with 10a-g