Polarit?t bin?rer L?sungsmittelgemische: Bestimmung von ET(30)-Werten und Korrelation mit kinetischen L?sungsmittel-Effekten

Zusammenfassung Zur empirischen Beschreibung der Polarität binärer Lösungsmittelgemische wurden mit einem solvatochromen Betain-Farbstoff E_T-Werte für folgende Systeme bestimmt: Methanol/Butanol-2, Methanol/2-Methylbutanol-2, Methanol/Pyridin, Methanol/Acetonitril, Methanol/Toluol und Ethanol/ 2,2,2-Trifluorethanol. In allen Systemen treten mehr oder weniger starke Abweichungen vom idealen Mischungsverhalten auf, was im einzelnen diskutiert wird. In den genannten Lösungsmittelgemischen wurde parallel die Kinetik der Ligandensubstitution an einem neutralen Kupfer(II)-bis-chelatkomplex vermessen. Die E_T-Werte korrelieren mit den lnkWerten (k = Geschwindigkeitskonstante für den durch das Solvens induzierten Ligandenaustausch). Dies weist darauf hin, daß die Bildung des Übergangszustandes durch H-Brücken erleichtert wird.

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Polarity of binary solvent mixtures: Determination of E_T(30)-values and correlation with kinetic solvent effects

Summary The polarity of binary solvent mixtures is empirically described by E_T-values as determined with a solvatochromic betaine dye. The following mixtures were studied: methanol/butanol-2, methanol/2-methylbutanol-2, methanol/pyridine, methanol/acetonitrile, methanol/toluene and ethanol/2,2,2-trifluoroethanol. All mixtures behave as more or less non-ideal systems which is discussed in detail. Parallel to the determination of E_T-values the kinetics of ligand substitution in a neutral copper(II)-bis-chelate complex were studied in the same set of solvent mixtures. The E_T-values correlate with the corresponding lnk-values (k = rate constant for solvent induced ligand substitution). This would mean that the formation of the transition state is facilitated by hydrogen bonding.

Für finanzielle Unterstützung bedanken wir uns bei der Deutschen Forschungsgemeinschaft und dem Verband der Chemischen Industrie e.V. Der verwendete Salicylaldehyd wurde uns von der Firma Bayer AG, Leverkusen, zur Verfügung gestellt.     

Shape evolution of detached Bridgman crystals grown in microgravity

Detached (or dewetted) Bridgman crystal growth defines that process in which a gap exists between a growing crystal and the crucible wall. In microgravity, the parameters that influence the existence of a stable gap are the growth angle of the solidifying crystal, the contact angle between the melt and the crucible wall, and the pressure difference across the meniscus. During actual crystal growth, the initial crystal radius will not have the precise value required for stable detached growth. Beginning with a crystal diameter that differs from stable conditions, numerical calculations are used to analyze the transient crystal growth process. Depending on the initial conditions and growth parameters, the crystal shape will either evolve towards attachment at the crucible wall, towards a stable gap width, or inwards towards eventual collapse of the meniscus. Dynamic growth stability is observed only when the sum of the growth and contact angles exceeds 180°.     

Niederkoordinierte Phosphor-Verbindungen. 42. Trennung und röntgenographische Strukturbestimmung der E,Z-Isomeren des 2,4,6-Tri(tert.butyl)phenyl-phenylmethylenphosphans

Low-Coordinated Phosphorus Compounds. 42. Separation and Structure Determination by X-Ray of the E,Z-Isomers of 2,4,6-Tri(tert.butyl)phenyl-phenylmethylenphosphaalkene The E,Z-isomers of phosphaalkenes can be separated by fractional crystallisation and HPLC. The structures of the E,Z-forms of the phosphaalkene 2a have been proved by X-ray determination.     

Conformations in dioctyl substituted polyfluorene: a combined theoretical and experimental Raman scattering study

The structural properties of polyfluorenes (PF) are extremely sensitive to the choice of functionalizing side chains. Dioctyl substituted PF (PF8) adopts metastable structures that depend upon the thermal history and choice of solvents used in film forming conditions. We present a detailed study of the changes in the backbone and side chain morphology in PF8, induced by the various crystallographic phases, using Raman scattering techniques. The vibrational frequencies and intensities of fluorene oligomers are calculated using hybrid density-functional theory with a 3-21G(*) basis set. The alkyl side chains are modeled as limiting conformations: all anti, anti-gauche-gauche, and end gauche representations. The calculated vibrational spectra of single chain oligomers in conjunction with our experimental results demonstrate the beta phase, which is known to originate in regions of enhanced chain planarity as a direct consequence of the alkyl side chain conformation.     

A Modular Class of Fluorescent Difluoroboranes: Synthesis,Structure, Optical Properties,Theoretical Calculations and Applications for Biological Imaging

Ten borylated bipyridines (BOBIPYs) have been synthesized and selected structural modifications have been made that allow useful structure–optical property relationships to be gathered. These systems have been further investigated using DFT calculations and spectroscopic measurements, showing blue to green fluorescence with quantum yields up to 41 %. They allow full mapping of the structure to determine where selected functionalities can be implemented, to tune the optical properties or to incorporate linking groups. The best derivative was thus functionalised with an alkyne linker, which would enable further applications through click chemistry and in this optic, the stability of the fluorophores has been evaluated.