Universität Stuttgart
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Item Open Access Optical detection of magnetic resonance (ODMR) of naphthalenophanes(1981) Schweitzer, Dieter; Hausser, Karl H.; Blank, Norman E.; Haenel, Matthias-Item Open Access Optical detection of magnetic resonance (ODMR) of triple-layered phanes(1981) Melzer, Guenter; Schweitzer, Dieter; Hausser, Karl H.; Staab, Heinz A.; Zapf, Udo-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 Investigation of the excited triplet states of [2.2]- and [3.3]paracyclophane(1979) Melzer, Guenter; Schweitzer, Dieter; Hausser, Karl H.; Colpa, Johannes Pieter; Haenel, MatthiasWe have studied the excited triplet states of [2-2]- and [3.3]paracyclophane by emission spectroscopy and by ODMR and have compared the results with the corresponding monomer paraxylene. The most striking result is that both phanes exhibit two sets of zero field splitting parameters indicating the existence of two nearly degenerate low lying excited triplet states. Furthermore, we find in distinction to expection a stronger reduction of the zero field splitting parameters as compared to the monomers for [3.3]paracyclophane than for [2.2]paracyclophane. The causes of these surprising experimental findings are discussed.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 Spin rotation interaction and anisotropic chemical shift in 13CS2(1971) Spiess, Hans Wolfgang; Schweitzer, Dieter; Haeberlen, Ulrich; Hausser, Karl H.The 13C nuclear spin-lattice relaxation time T1 was studied in liquid CS2 from -106°C to +35°C at resonance frequencies of 14, 30, and 62 MHz. The relaxation is caused by anisotropic chemical shift and spin-rotation interaction. It is shown that for linear molecules the spin-rotation constant C and the anisotropy of the chemical shift Δσ can be obtained from the relaxation rates without use of adjustable parameters. The analysis yields: C = -13.8 ± 1.4 kHz and Δσ = 438 ± 44 ppm.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 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 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 Influence of an identified dimer vibration on the emission spectrum of [2,2]paracyclophane(1980) Goldacker, Wilfried; Schweitzer, Dieter; Dinse, Klaus Peter; Hausser, Karl H.The emission spectrum of polycrystalline [2,2]paracylophane shows a resolved vibronic structure with a 241 cm−1 progression at He temperatures. The dependence of the energy of this mode upon selective deuteration in combination with results from FIR and Raman spectra could be used to identify the mode as a torsional dimer vibration. The emission spectra could be simulated assuming a linear coupling of the torsional mode to the electronic transitions with coupling strengths of S = 10 (fluorescence) and S = 13 (phosphorescence). This corresponds to an equilibrium displacement of the benzene rings under electronic excitation by a torsional angle of 10.6° (S1) and 12.1° (T1), in addition to the small torsion in the ground state S0 by about 3°.