In this paper, we report on the synthesis of 0-carotenes of variable chain length with between 5 and 23 double bonds (1-7). These oligoenes were prepared by McMurry and Wittig reactions. The tetradecapreno-P-carotene ? would seem to be the longest 0-carotene yet reported. Furthermore, we investigated the electronic properties using cyclic voltammetry and photoelectron spectroscopy (UPS) to generate openshell and closed-shell ions of carotenoids in solution and in the solid state, respectively. With increasing chain length ( 2 11 double bonds), even the generation of tetracations and tetraanions could be observed by cyclic voltammetry. Extending the number of conjugated bonds causes the potentials to converge to limiting values. All electron-transfer processes occur in one-electron steps, which are close to each other in pairs. The potential difference between the first oxidation potential and the first reduction potential is a linear function of the reciprocal chain length. Despite the different techniques used (CV and UPS) and the different condensed phases, there is an excellent correspondence between the energies of the radical cation states generated by the two methods. This shows that the radical cation formation is principally determined by the chain length. The structures of the ion states were investigated using semiempirical methods at the NDDO level. Charge delocalization and bond relaxation are not identical and do not utilize the same number or the same kind of atoms. It can be shown that from the length of 20 double bonds onwards, the effective conjugation length for doubly-charged cations converges slowly to a limiting value.

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Vinylogous β-Carotenes: Generation, Storage, and Delocalization of Charge in Carotenoids.-The β-carotenes (I)-(IV) of variable chain length containing 5-23 double bonds are synthesized by McMurry and Wittig reactions. The generation of open-shell and closed-shell ions of carotenoids in solution and in the solid state is investigated by cyclic voltammetry and photoelectron spectroscopy. The potential difference between the first oxidation potential and the first reduction potential is a linear function of the reciprocal chain length. An excellent correspondence between the energies of the radical cation states by the 2 methods is observed showing that the formation of radical cations is principally determined by the chain length. -(BROSZEIT, G.; DIEPENBROCK, F.; GRAEF, O.; HECHT, D.; HEINZE, J.; MARTIN, H.-D.; MAYER, B.; SCHAPER, K.; SMIE, A.; STREHBLOW, H.-H.; Liebigs Ann.