Ortho- and edge-functionalization of ryleneimides
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Abstract
In this thesis new synthetic methods were developed that ebable the selective functionalization of the “unconventional” positions of ryleneimides. Those positions are molecular sites that cannot be selectively addressed via the established halogenation and imidization reactions, namely 1) the sites ortho to the imide groups, known also as ortho-positions; 2) the 8,11-positions of perylenemonoimides, defined here as edge-positions. Focusing on derivatives of perylenediimides (PDI), terrylenediimides (TDI) and perylenemonoimides (PMI), the impact of the ortho- and edge-functionalization was explored. Via the introduction of a broad variety of substituents the solubility, optical and electrochemical properties of ryleleimides could be tailored. Via the introduction of alkyl substituents in the ortho-positions, solubility and solid state packing could be tuned. In this way novel electron acceptors for fullerene-free bulk heterojunction solar cells could be synthesized. A way for the synthesis of a stable lactonized quinoidal PMI derivative was also investigated. Furthermore novel building blocks provided a toolbox of precursors allowing a broader range of funtionalization, such as tetracyano-PDI and -TDI. Such strong planar electron acceptors were investigated as n-type semiconductors for organig field effect transistors. The impact of ortho- and bay-tetrafunctionalization was investigated comparing two TDI derivatives. Finally the succesfull edge-functionalization of PMI provided a synthetic route to innovative light absorbers for dye-sensitized solar cells.