The photophysics of the three transition metal phthalocyanines NiPc, CuPc and ZnPc in their β-phase has been studied using complementary experimental techniques: photoluminescence, optical absorption and electronenergy-loss spectroscopy. We demonstrate that the strongly different photoluminescence signal can be understood based on the different exciton dispersions, and that tiny differences in the structure and thus the intermolecular orbital overlap is able to model these differences. Our results clearly indicate a significant admixture of charge-transfer excitations to the lowest exciton state. They additionally demonstrate the need of a detailed microscopic understanding of organic semiconductors for their application potential.

High-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure—unknown before—was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes.

The electronic excitation spectrum of -CuPc has been investigated using electron energy-loss spectroscopy in transmission. Our results demonstrate a rather strong momentum dependence of the lowest exciton features. Both main components show a negative dispersion, and the momentum dependence indicates that this negative dispersion is parallel to the molecular stacks in-CuPc. In addition, the spectral shape also varies upon increasing momentum transfer indicating a particular momentum dependence of the inter-molecular interactions.

With the aim of pushing the knowledge and understanding on mixed films of organic semiconductors forward, blends of ZnPC and F8ZnPC in different ratios are manufactured. The films have a polycrystalline structure, as indicated by electron diffraction profiles and infrared-spectroscopy. Photoluminescence data show completely different spectra for the blends, compared to the pure materials, which can be ascribed to the suppressing of excimer formation and the appearance of a new charge-transfer excitation between the two different molecules in the blends. This new excitation can also be seen in optical absorption. Momentum dependent measurements of the electronic excitations by electron energy-loss spectroscopy confirm the localized character of the new charge-transfer excitation in the blends. Our experimental data help understand the important issue of donor/acceptor coupling in organic semiconductors.

Mononuclear and polymeric Co(II) complexes were obtained with enantiopure and racemic N-thiophosphorylated thioureas with the metal to ligands ratio 1:2. To control the stereochemistry of the complexes synthesized from racemic...