Ge2Co6(CO)20: Ein Ge‐Co‐Cluster ausgehend von gelöstem GeBr

Ge₂Co₆(CO)₂₀: A Ge‐Co Cluster Compound from Solubilized GeBr The Ge‐Co cluster Ge₂Co₆(CO)₂₀ is synthesized from a reaction of a GeBr solution with Co₂(CO)₈. Isolation of suitable crystals allows the determination of the crystal structure of Ge₂Co₆(CO)₂₀, being the lacking member in the row GeCo₄(CO)₁₄ – Ge₂Co₆(CO)₂₀ – Ge₃Co₈(CO)₂₆.     

Efficient synthesis of unsymmetrical sulfamides from sulfamic acid salts by activation with triphenylphosphine ditriflate

A general approach to prepare unsymmetrical sulfamides is described. This method relies on the activation of sulfamic acid salts with triphenylphosphine ditriflate, and subsequent trapping by a nucleophilic amine. This strategy improves access to N-octadecyl-N′-propylsulfamide, a feeding suppressant.     

Metal-Organic Frameworks as Hosts for Fluorinated Azobenzenes: A Path towards Quantitative Photoswitching with Visible Light

Fifteen new photochromic hybrid materials were synthesized by gas phase loading of fluorinated azobenzenes, namely ortho-tetrafluoroazobenzene (tF-AZB), 4H,4H′-octafluoroazobenzene (oF-AZB), and perfluoroazobenzene (pF-AZB), into the pores of the well-known metal-organic frameworks MOF-5, MIL-53(Al), MIL-53(Ga), MIL-68(Ga), and MIL-68(In). Their composition was analysed by elemental (CHNS) and DSC/TGA. For pF-AZB_0.34@MIL-53(Al), a structural model based on high-resolution synchrotron powder diffraction data was developed and the host-guest and guest-guest interactions were elucidated from this model. These interactions of O−H⋅⋅⋅F and π⋅⋅⋅π type were confirmed by significant shifts of the O−H frequencies in loaded and unloaded MOFs of the MIL-53 and MIL-68 series. Most remarkably, all of the synthesized F-AZB@MOF systems can be switched with visible light, and some of them show almost quantitative (>95 %) photo-isomerization between its E and Z forms with no significant fatigue after repeated switching cycles.     

Do Docking Sites Persist Upon Fluorination? The Diadamantyl Ether-Aromatics Challenge for Rotational Spectroscopy and Theory

Fluorinated derivatives of biological molecules have proven to be highly efficient at modifying the biological activity of a given protein through changes in the stability and the kind of docking interactions. These interactions can be hindered or facilitated based on the hydrophilic/hydrophobic character of a particular protein region. Diadamantyl ether (C₂₀H₃₀O) possesses both kinds of docking sites, serving as a good template to model these important contacts with aromatic fluorinated counterparts. In this work, an experimental study on the structures of several complexes between diadamantyl ether and benzene as well as a series of fluorinated benzenes is reported to analyze the effect of H→F substitution on the interaction and structure of the resulting molecular clusters using rotational spectroscopy. All experimentally observed complexes are largely dominated by London dispersion interactions with the hydrogen-terminated surface areas of diadamantyl ether. Already single substitution of one hydrogen atom with fluorine changes the preferred docking site of the complexes. However, the overall contributions of the different intermolecular interactions are similar for the different complexes, contrary to previous studies focusing on the difference in interactions using fluorinated and non-fluorinated molecules.     

The influence of topography on dynamic wetting

The paramount importance of wetting applications and the significant economic value of controlling wetting-based industrial processes has stimulated a deep interest in wetting science. In many industrial applications the motion of a complex liquid front over nano-textured surfaces controls the fate of the processes. However our knowledge of the impact of nano-heterogeneities on static and dynamic wetting is very limited. In this article, the fundamentals of wetting are briefly reviewed, with a particular focus on hysteresis and roughness issues. Present knowledge and models of dynamic wetting on smooth and rough surfaces are then examined, with particular attention devoted to the case of nano-topographical heterogeneities and solid–fluid–fluid systems.     

A Nonaqueous Redox-Matched Flow Battery with Charge Storage in Insoluble Polymer Beads**

We describe the nonaqueous redox-matched flow battery (RMFB), where charge is stored on redox-active moieties covalently tethered to non-circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high-solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox-matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox-active moieties via attachment to the versatile Merrifield resin.