Search results for "MOS"
showing 10 items of 10534 documents
Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au III Compounds: New Mechanistic Insights
2020
To gain more insight into the factors controlling the efficient cysteine arylation by cyclometalated Au(III) complexes, the reaction between selected gold compounds and different peptides was investigated by high‐resolution liquid chromatography electrospray ionization mass spectrometry (HR‐LC‐ESI‐MS). The deducted mechanisms of C–S cross‐coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.
An investigation of photo- and pressure-induced effects in a pair of isostructural two-dimensional spin-crossover framework materials
2014
International audience; Two new isostructural iron(II) spin-crossover (SCO) framework (SCOF) materials of the type [Fe(dpms)2 (NCX)2 ] (dpms=4,4'-dipyridylmethyl sulfide; X=S (SCOF-6(S)), X=Se (SCOF-6(Se))) have been synthesized. The 2D framework materials consist of undulating and interpenetrated rhomboid (4,4) nets. SCOF-6(S) displays an incomplete SCO transition with only approximately 30 % conversion of high-spin (HS) to low-spin iron(II) sites over the temperature range 300-4 K (T1/2 =75 K). In contrast, the NCSe(-) analogue, SCOF-6(Se), displays a complete SCO transition (T1/2 =135 K). Photomagnetic characterizations reveal quantitative light- induced excited spin-state trapping (LIES…
Thermo-Chromium: A Contactless Optical Molecular Thermometer.
2017
The unparalleled excited-state potential-energy landscape of the chromium(III)-based dye [1]3+ ([Cr(ddpd)2 ]3+ ; ddpd=N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridin-2,6-diamine) enables a strong dual emission in the near infrared region. The temperature dependence of this dual emission allows the use of [1]3+ as an unprecedented molecular ratiometric thermometer in the 210-373 K temperature range in organic and in aqueous media. Incorporation of [1]3+ in biocompatible nanocarriers, such as 100 nm-sized polystyrene nanoparticles and solutol micelles, provides nanodimensional thermometers operating under physiological conditions.
Synthesis, crystal structure and magnetic properties of [Co(bpcam)2]ClO4·dmso·H2O, [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O and [Ni(bpcam)2]·H2O [Hbpcam = bi…
2017
The preparation, spectroscopic characterization, structural study and magnetic investigation of three new complexes of formula [Co(bpcam)2]ClO4·dmso·H2O (1), [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O (2) and [Ni(bpcam)2]·H2O (3) [Hbpcam = bis(2-pyrimidylcarbonyl)amide] are reported. Each bpcam group in 1–3 acts as a tridentate ligand being coordinated to the cobalt(III) (1 and 2)/nickel(II) (3) ions through three nitrogen atoms in a mer-arrangement. Six-coordinate cobalt(III) and nickel(II) occur in 1 and 3 respectively, whereas six-coordinate cobalt(III) and four-coordinate cobalt(II) coexist in 2. Cyclic voltammetry of 1 in acetonitrile shows the occurrence of one quasi reversible CoIII ↔ CoII pro…
The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(ii) complexes: dual excited state deactivation and dual emission
2016
The synthesis and characterization of a series of weakly emissive mononuclear cyclometalated [Ru(dpb-R)(tpy)](+) complexes with functional groups R of varying electron-donating characters at the dpb ligand are described (dpbH = 1,3-di(2-pyridyl)benzene, tpy = 2,2';6',2''-terpyridine, 1(+): R = NHCOMe, 2(+): R = NH2, 3(+): R = COOEt, 4(+): R = COOH). Steady-state emission spectroscopy in the temperature range between 298 K and 77 K revealed a previously unrecognized excited state deactivation pathway via low-lying triplet ligand-to-ligand ((3)LL'CT) charge transfer states in addition to the well-known pathway via(3)MC states. Thermal activation barriers for depopulation of the emissive metal…
On the magneto-structural role of the coordinating anion in oxamato-bridged copper(ii) derivatives
2019
We herein present the synthesis, spectroscopic analysis, description of the crystal structures and magnetic properties of four new complexes of the formula [{Cu(opba)(H2O)1.2}{Cu(dmphen)(SCN)}2]·dmf (1), [{Cu(opba)}2{Cu(dmphen)Cl}4]·1.5dmf·2.5dmso (2), [{Cu(opba)}2{Cu(dmphen)Br}4]·dmf·2.3dmso (3) and [{Cu(opba)}{Cu(dmphen)(dca)}2]n (4) [H4opba = N,N′-1,2-phenylenebis(oxamic acid), dmphen = 2,9-dimethyl-1,10-phenanthroline and dca = dicyanamide anion]. 1 is a neutral tricopper(II) complex where an inner [Cu(opba)]2− fragment adopts a bis-bidentate coordination mode towards two outer [Cu(dmphen)(NCS)]+ units. 2 and 3 are bis-trinuclear species where two oxamato-bridged [Cu(opba){Cu(dmphen)X}2…
Quasi-geostrophic jet-like flow with obstructions
2021
International audience; Jet-like flows are ubiquitous in the atmosphere and oceans, and thus a thorough investigation of their behaviour in rotating systems is fundamental. Nevertheless, how they are affected by vegetation or, generally speaking, by obstructions is a crucial aspect which has been poorly investigated up to now. The aim of the present paper is to propose an analytical model developed for jet-like flows in the presence of both obstructions and the Coriolis force. In this investigation the jet-like flow is assumed homogeneous, turbulent and quasi-geostrophic, and with the same density as the surrounding fluid. Laws of momentum deficit, length scales, velocity scales and jet cen…
The MIRS computer package for modeling the rovibrational spectra of polyatomic molecules
2003
International audience; The MIRS spectroscopic software for the modeling of ro-vibrational spectra of polyatomic molecules is presented. It is designed for the global treatment of complex band systems of molecules to take full account of symmetry properties. It includes e cient algorithms based on the irreducible tensor formalism. Predictions and simultaneous data fi tting (positions and intensities) are implemented as well as advanced options related to group theory algebra. Illustrative examples on CH3D, CH4, CH3Cl and PH3 are reported and the present status of data available is given. It is written in C++ for standard PC computer operating under Windows. The full package including on-lin…
Thermodynamic correction of particle concentrations measured by underwing probes on fast flying aircraft
2016
Abstract. Particle concentration measurements with underwing probes on aircraft are impacted by air compression upstream of the instrument body as a function of flight velocity. In particular for fast-flying aircraft the necessity arises to account for compression of the air sample volume. Hence, a correction procedure is needed to invert measured particle number concentrations to ambient conditions that is commonly applicable for different instruments to gain comparable results. In the compression region where the detection of particles occurs (i.e. under factual measurement conditions), pressure and temperature of the air sample are increased compared to ambient (undisturbed) conditions i…
Computational Study of the Effect of Glyoxal–Sulfate Clustering on the Henry’s Law Coefficient of Glyoxal
2014
We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic…