Mechanistic insights and kinetic analysis for the oxidative hydroxylation of arylboronic acids by visible light photoredox catalysis: a metal-free alternative.

The photocatalytic hydroxylation of boronic acids with methylene blue as photosensitizer proceeds with high efficiency. Detailed time-resolved studies of the relevant rate constants provide a clear mechanistic understanding of excited-state processes and guided the selection of the photocatalyst and the optimization of experimental conditions.

Photoinduced carbene generation from diazirine modified task specific phosphonium salts to prepare robust hydrophobic coatings.

3-Aryl-3-(trifluormethyl)diazirine functionalized highly fluorinated phosphonium salts (HFPS) were synthesized, characterized, and utilized as photoinduced carbene precursors for covalent attachment of the HFPS onto cotton/paper to impart hydrophobicity to these surfaces. Irradiation of cotton and paper, as proof of concept substrates, treated with the diazirine-HFPS leads to robust hydrophobic cotton and paper surfaces with antiwetting properties, whereas the corresponding control samples absorb water readily. The contact angles of water were determined to be 139° and 137° for cotton and paper, respectively.

Photoactivated nitrene chemistry to prepare gold nanoparticle hybrids with carbonaceous materials.

Photolysis of organic solvent soluble aryl azide-modified gold nanoparticles (N(3)-AuNPs) with a core size of 4.6±1.6 nm results in the generation of interfacial reactive nitrene intermediates.

Michael addition reactions for the modification of gold nanoparticles facilitated by hyperbaric conditions.

The chemical interfacial modification of organic solvent soluble 2.4 ± 0.5 nm maleimide-modified monolayer protected gold nanoparticles (2-C(12)AuNPs) with primary or secondary amines via Michael addition reactions is demonstrated.

Light-activated covalent formation of gold nanoparticle-graphene and gold nanoparticle-glass composites.

Monolayer protected gold nanoparticles (AuNPs) modified with a 3-aryl-3-(trifluoromethyl)diazirine functionality at its terminus (Diaz-AuNPs, 3.9 nm) were prepared and irradiated in the presence of two very different substrates, reduced graphene and glass. Upon irradiation, the terminal diazirine group loses nitrogen to generate a reactive carbene at the interface of the AuNPs that can then undergo addition or insertion reactions with functional groups on the graphene or glass surfaces, leading to the formation of graphene-AuNP and glass-AuNP hybrids, respectively.

Covalent diamond-gold nanojewel hybrids via photochemically generated carbenes.

Photochemical generation of a reactive carbene-modified gold nanoparticle (AuNP) in the presence of micro-diamond monocrystalline powder leads to a robust covalent diamond-AuNP hybrid material.

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.