Universität Stuttgart
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Item Open Access Transanular interaction in [2.2]phanes: models for dimers?(1979) Goldacker, Wilfried; Hausser, Karl H.; Schweitzer, Dieter; Staab, Heinz A.The emission spectra of pseudo-ortho 3 and pseudo-geminal-4,7,12,15-tetramethoxy[2.2]-paracyclophane 3 were measured in glass matrices at 1.3 K. Furthermore, the zero field splitting parameters D and E and the decay rate constants ki of the excited triplet state were studied by optical detection of magnetic resonance in zero field. The results were compared with the corresponding monomer 1,4-dimethyl-2,5-dimethoxybenzene.Item Open Access ODMR of phanes and charge transfer phanes(1979) Schweitzer, Dieter; Goldacker, Wilfried; Hausser, Karl H.; Staab, Heinz A.Triplet zero field splitted parameters |D| and |E| and decay rates ki of the triplet sublevels of two stereoisomeric tetramethoxy [2.2] paracyclophanes as well as those of two CT [2.2] paracyclophanes in low concentration in glasses and small neat single ctystals as measured by ODMR in zero fields at 1,3 K are presented.Item Open Access Transanular interaction in [2.2]phanes: [2.2](2,7)pyrenophane(1976) Schweitzer, Dieter; Hausser, Karl H.; Kirrstetter, Reiner G. H.; Staab, Heinz A.The emission spectra of [2.2](2,7)pyrenophane and the zero field splitting parameters D and E of its excited triplet state were measured in glasses and in small single crystals at 1.3 K. The results are being compared with monomer pyrene and 2,7 dimethylpyrene in liquid and solid solutions as well as in single crystals.Item Open Access Transannular interactions in [2.2] phanes as studied by magnetic resonance and optical spectra(1975) Schweitzer, Dieter; Colpa, Johannes Pieter; Behnke, J.; Hausser, Karl H.; Haenel, Matthias; Staab, Heinz A.The interaction of π-electrons in [2.2] phanes was studied both experimentally and theoretically. The fluorescence and phosphorescence spectra were measured at liquid helium temperature; in addition, the zero field splitting parameters D and E were determined by ODMR in zero field and by ordinary ESR at X-band. The results for the phanes with two identical aromatic units can be summarized as follows: The rather small reduction of the D and E values of the order of 10% with respect to the monomers indicates, in agreement with the theoretical treatment given in part II, that the two unpaired electrons of the excited triplet state have a high probability to be at a given time in the same half of the molecule. While the fluorescence spectra show the typical behaviour of emission spectra of dimers or excimers, the phosphorescence spectra exhibit some remaining structure. This behaviour which indicates a somewhat weaker coupling among the triplet orbitals as compared to the singlet orbitals can also be understood on the basis of theoretical considerations. For a phane with two different aromatic units the behaviour is found to be more similar to the corresponding aromatic monomer with the lower excited states with some perturbation by the other part of the phase also in agreement with theoretical expectation.Item Open Access Molecular structure and spectroscopic properties of Kekulene(1979) Krieger, Claus; Diederich, Francois; Schweitzer, Dieter; Staab, Heinz A.Considerable bond localization has been detected in kekulene(1) by X-ray structure analysis: only every second ring is "aromatic". This initially surprising result is in accord with various spectroscopic properties of (1).Item Open Access Electronic properties of two isomeric charge transfer [2.2]paracyclophanes(1976) Schweitzer, Dieter; Hausser, Karl H.; Taglieber, Volker; Staab, Heinz A.The emission spectra and the zero field splitting parameters of the two diastereomeric 4,7-dicyano-12,15-dimethoxy-[2.2] paracyclophanes 3 and 4 in comparison to the corresponding monomers 1 and 2 were investigated in order to study the orientation dependence of charge transfer (CT) interactions. The general results in glasses (PMMA) are: broad structureless emission bands with large spectral overlap between fluorescence and phosphorescence; strong reduction of the zero field splitting parameters D and D* by a factor of two for the pseudo-ortho isomer 3 and by a factor of four for the pseudo-geminal isomer 4 showing the strong effect of the geometrical orientation. In single crystals of the same phanes the zero field parameters were found to be further reduced to about one fifth of the value of the monomers which indicates, in accordance with the emission spectra, an additional intermolecular interaction between adjacent phanes.Item Open Access Transannular interactions in [2.2] phanes as studied by luminescence and optical detection of magnetic resonance(1976) Schweitzer, Dieter; Colpa, Johannes Pieter; Hausser, Karl H.; Haenel, Matthias; Staab, Heinz A.Emission spectra of different types of [2.2] naphthalenophanes were measured at 1.25 K in glasses as well as in small single crystals. In addition, the D and E values of the excited triplet states were studied by optical detection of magnetic resonance in zero field and the results compared with the corresponding monomeres.Item Open Access Molekülstruktur und spektroskopische Eigenschaften des Kekulens(1979) Krieger, Claus; Diederich, Francois; Schweitzer, Dieter; Staab, Heinz A.Beträchtliche Bindungslokalisation im Kekulen (1) wurde durch Röntgen-Strukturanalyse nachgewiesen: Nur jeder zweite Ring ist "aromatisch". Dieser zunächst überraschende Befund ist mit einigen spektroskopischen Eigenschaften von (1) in Einklang.