Syntheses, x-ray structures, photochemistry, redox properties, and DFT calculations of interconvertible fac- and mer-[Mn(SPS)(CO)3] isomers containing a flexible SPS-based pincer ligand

The lithium salt of the anionic SPS pincer ligand composed of a central hypervalent lambda(4)-phosphinine ring bearing two ortho-positioned diphenylphosphine sulfide side arms reacts with [Mn(CO)(5)Br] to give fac-[Mn(SPS)(CO)(3)], This isomer can be converted photochemicaily to mer-[Mn(SPS)(CO)(3)], with a very high quantum yield (0.80 +/- 0.05). The thermal backreaction is slow (taking ca. 8 h at room temperature), in contrast to rapid electrodecatalyzed mer-to-fac isomerization triggered by electrochemical reduction of mer-[Mn(SPS)(CO)(3)]. Both geometric isomers of [Mn(SPS)(CO)(3)] have been characterized by X-ray crystallography. Both isomers show luminescence from a low-lying (IL)-I-3 (SPS-based) excited state. The light emission of fac-[Mn(SPS)(CO)(3)] is largely quenched by the efficient photoisomerization occurring probably from a low-lying Mn-CO dissociative excited state. Density functional theory (DFT) and time-dependent DFT calculations describe the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of fac- and mer-[Mn(CO)(3)(SPS)] as ligand-centered orbitals, largely localized on the phosphinine ring of the SPS pincer ligand. In line with the ligand nature of its frontier orbitals, fac-[Mn(SPS)(CO)(3)] is electrochemically reversibly oxidized and reduced to the corresponding radical cation and anion, respectively. The spectroscopic (electron paramagnetic resonance, IR, and UV-vis) characterization of the radical species provides other evidence for the localization of the redox steps on the SIPS ligand. The smaller HOMO-LUMO energy difference in the case of mer-[Mn(CO)(3)(SPS)], reflected in the electronic absorption and emission spectra, corresponds with its lower oxidation potential compared to that of the fac isomer. The thermodynamic instability of mer-[Mn(CO)(3)(SPS)], confirmed by the DFT calculations, increases upon one-electron reduction and oxidation of the complex.

The interdependence of continental warm cloud properties derived from unexploited solar background signals in ground-based lidar measurements

We have extensively analysed the interdependence between cloud optical depth, droplet effective radius, liquid water path (LWP) and geometric thickness for stratiform warm clouds using ground-based observations. In particular, this analysis uses cloud optical depths retrieved from untapped solar background signals that are previously unwanted and need to be removed in most lidar applications. Combining these new optical depth retrievals with radar and microwave observations at the Atmospheric Radiation Measurement (ARM) Climate Research Facility in Oklahoma during 2005–2007, we have found that LWP and geometric thickness increase and follow a power-law relationship with cloud optical depth regardless of the presence of drizzle; LWP and geometric thickness in drizzling clouds can be generally 20–40 % and at least 10 % higher than those in non-drizzling clouds, respectively. In contrast, droplet effective radius shows a negative correlation with optical depth in drizzling clouds and a positive correlation in non-drizzling clouds, where, for large optical depths, it asymptotes to 10 μm. This asymptotic behaviour in non-drizzling clouds is found in both the droplet effective radius and optical depth, making it possible to use simple thresholds of optical depth, droplet size, or a combination of these two variables for drizzle delineation. This paper demonstrates a new way to enhance ground-based cloud observations and drizzle delineations using existing lidar networks.