Tuning of redox potentials by introducing a cyclometalated bond to bis-tridentate ruthenium(II) complexes bearing bis(N-methylbenzimidazolyl)benzene or -pyridine ligands

A series of asymmetrical bis-tridentate cyclometalated complexes including [Ru(Mebib)(Mebip)](+), [Ru(Mebip)(dpb)](+), [Ru(Mebip)(Medpb)](+), and [Ru(Mebib)(tpy)](+) and two bis-tridentate noncyclometalated complexes [Ru(Mebip)(2)](2+) and [Ru(Mebip)(tpy)](2+) were prepared and characterized, where Mebib is bis(N-methylbenzimidazolyl)benzene, Mebip is bis(N-methylbenzimidazolyl)pyridine, dpb is 1,3-di-2-pyridylbenzene, Medpb is 4,6-dimethyl-1,3-di-2-pyridylbenzene, and tpy is 2,2':6',2″-terpyridine. The solid-state structure of [Ru(Mebip)(Medpb)](+) is studied by X-ray crystallographic analysis. The electrochemical and spectroscopic properties of these ruthenium complexes were studied and compared with those of known complexes [Ru(tpy)(dpb)](+) and [Ru(tpy)(2)](2+). The change of the supporting ligands and coordination environment allows progressive modulation of the metal-associated redox potentials (Ru(II/III)) from +0.26 to +1.32 V vs Ag/AgCl. The introduction of a ruthenium cyclometalated bond in these complexes results in a significant negative potential shift. The Ru(II/III) potentials of these complexes were analyzed on the basis of Lever's electrochemical parameters (E(L)). Density functional theory (DFT) and time-dependent DFT calculations were carried out to elucidate the electronic structures and spectroscopic spectra of complexes with Mebib or Mebip ligands.     

Stimulated Brillouin scattering in dispersion-decreasing fiber with ultrahigh-speed femtosecond soliton pulse compression

We report that stimulated Brillouin scattering (SBS) in a dispersion-decreasing fiber (DDF) is particularly disadvantageous with ultrahigh-speed femtosecond soliton compression that exceeds 40 GHz. It is important to note that the increase in the longitudinal mode power of a soliton is proportional to the square of the repetition rate. The SBS threshold is determined by the dispersion-decreasing rate of the DDF, rather than its fiber loss. We suppressed the SBS by applying 30-MHz frequency modulation to a mode-locked fiber laser and successfully obtained a stable 40-GHz, 100-fs pulse train.     

Elucidation of the stereochemistry of thiirane formation from a 1λ4,2‐dithietane bearing two chiral carbon centers

A tetracoordinated sulfurane bearing a 1λ⁴,2‐dithietane moiety, whose 3‐ and 4‐positions were chiral carbon centers, was synthesized. Its thermolysis gave the corresponding thiirane as a single diastereomer, whose configuration and stereochemistry were determined. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:412–417, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20630