NIR-emissive, singlet-oxygen-sensitizing gold tetra(thiocyano)corroles.

Presented herein are two fully characterized gold tetrathiocyanocorroles representing a potentially significant new class of NIR-emissive 5d-metallocorroles. The four SCN groups on the bipyrrole unit of the corrole exert a powerful electron-withdrawing effect, upshifting both the oxidation and reduction potentials by roughly half a volt relative to their unsubstituted counterparts. That said, the upshift of the LUMO is somewhat higher than that of the HOMO so these complexes also exhibit a smaller HOMO-LUMO gap, as evinced in both electrochemical measurements and Q band energies (∼595 nm relative to ∼571 nm for their SCN-free counterparts). The new compounds exhibit NIR phosphorescence under ambient conditions with emission maxima around 900 nm (compared with 790 nm for simple Au triarylcorroles), phosphorescence quantum yields around 0.3%, phosphorescence lifetimes around 10 µs, and singlet oxygen sensitization with a quantum yield of around 50 ± 5% in solution, together signifying wide-ranging potential applications as triplet photosensitizers in oxygen sensing and photodynamic therapy.

Synthesis, Characterization, and Application of Oxo-Molybdenum(V)-Corrolato Complexes in Epoxidation Reactions.

Sharpless et al. have described, while performing the molybdenum-catalyzed epoxidation reaction of olefins using alkyl hydroperoxides, that the molybdenum-oxo moiety is an active catalytic species. Thus, continuous efforts have been made to synthesize molybdenum-oxo complexes of different ligand environments. While plenty of such works on molybdenum porphyrins are reported in the literature, related molybdenum corroles are very less reported. The synthesis and characterization of two new oxo-molybdenum(V)-corrolato complexes are described herein. Both the complexes have been fully characterized by several spectroscopic techniques in conjunction with single-crystal X-ray diffraction analysis. The efficacy of the oxo-molybdenum(V)-corrolato complexes for the catalytic epoxidation reaction of olefins with the help of hydroperoxides has also been explored. The catalytic application of oxo-molybdenum(V)-corrolato complexes in the epoxidation reaction has not been reported earlier. A mechanism has been proposed to explain the experimental findings.