Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in i...

This Perspective presents recent advances in macromolecular engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concentrations of Cu catalysts and can be run in environmentally friendly media, e.g., water. The roles of the major components of ATRP--monomers, initiato...

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The rhenium(V) complex [(HCpz3)ReOCl2]+ ([1]+), the tris(pyrazolyl)methane analogue of the known tris(pyrazolyl)borate complex (HBpz3)ReOCl2 (2), has been prepared. The two complexes are strikingly similar, as are the phosphine oxide adducts [(HCpz3)ReCl2(OPPh3)]Cl ([3]Cl) and (HBpz3)ReCl2(OPPh3) (4), which have been characterized by X-ray crystallography. Comparison of the bimolecular reductio...

Overcoming the challenge of metal contamination in traditional ATRP systems, a metal-free ATRP process, mediated by light and catalyzed by an organic-based photoredox catalyst, is reported. Polymerization of vinyl monomers are efficiently activated and deactivated with light leading to excellent control over the molecular weight, polydispersity, and chain ends of the resulting polymers. Signifi...

The processes of ionization and energy transfer in a quantum system composed of two distant H atoms with an initial internuclear separation of 100 atomic units (5.29 nm) have been studied by the numerical solution of the time-dependent Schrödinger equation beyond the Born-Oppenheimer approximation. Thereby it has been assumed that only one of the two H atoms was excited by temporally and spatia...

The ring size effect of macrocyclic TMC ligands in nonheme iron(IV)-oxo complexes has been examined in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions; an iron(IV)-oxo complex bearing a smaller TMC ligand is more reactive in both HAT and OAT reactions, resulting from its high Fe(IV/III) redox potential.

An unprecedented silver-catalyzed formal insertion of arynes into Rf-I (Rf = CF3, C2F5) bonds has been developed. This protocol provides easy access to various ortho-perfluoroalkyl iodoarenes under mild conditions. In this insertion reaction, an ionic atom-transfer reaction of RfI occurs, and a silver-mediated metathesis process is involved in the efficient transfer of the electropositive iodin...

Density functional theory calculations were carried out to study the interaction of heroin molecule with pristine and N-dopedTiO2 anatase nanoparticles. The oxygen atom of heroin molecule was found to be the binding site on the heroin molecule. In contrast, the binding site of TiO2 nanoparticle was positioned over the fivefold coordinated titanium atoms. The results showed that the adsorption e...