For the synthesis of an ortho-dithienylpyrene, a K-region bromination of pyrene was developed which enabled the first reported, non-statistical asymmetric functionalization of pyrene at the 4, 5, 9 and 10 positions. Crystal structures, optical and electronic properties and FET characteristics have been investigated.

Donor and acceptor substituents were introduced at pyrene's K-regions in order to engineer its optoelectronic properties. A study of the influence of the substitution pattern on the frontier orbitals as well as on the molecular packing is provided. A comparison with the pure donor and acceptor substituted pyrene derivatives highlights the strong impact of the presented donor-acceptor substitution.

Based on modern pyrene chemistry, a new route toward the synthesis of the peri-pentacene framework was developed. Firstly, the tetraketo form as stable precursor was targeted, because the fully aromatic peri-pentacene is predicted to suffer from high instability and reactivity. Therefore, a recently developed 4,5,9,10-tetrafunctionalization of pyrene was utilized to build up a planar and a dragonfly-shaped derivative in five steps, which only differ in the two outer bonds between the peripheral benzene rings. The planar tetraketone could only be dissolved in strong acids upon protonation, which limited the use of analytical methods. In contrast, the dragonfly-shaped form showed excellent organosolubility. In-depth investigation by NMR spectroscopy revealed co-existence of atropo-isomers in solution. The optical and electronic properties were analyzed by UV/Vis spectroscopy and cyclic voltammetry. To approach aromatic conjugation, stepwise reduction in solution by using tetrabutylammonium borohydride was carried out. Reduced species were studied by ESR and UV/Vis spectroscopy, as well as by MALDI-TOF MS, confirming the formation of the radical anion.

PCR was successfully implemented into polymer chemistry to produce linear multiblock structures up to pentablock architectures. Salient features of the generated DNA polymer hybrids were the ultrahigh molecular weights and their structural accuracy. Besides pushing the limits in block copolymer synthesis. a highly sophisticated characterization of the DNA/synthetic polymer hybrids was carried out by scanning force microscopy (SFM). Direct visualization revealed single polymer chains with the expected contour lengths for the DNA blocks and a characteristic kink at the central organic polymer unit bridging them. Furthermore, DNA triblock copolymers were manipulated by SFM, which so far has only been demonstrated for neat DNA and dendronized polymers. Upon blowing circular topologies, the DNA and the organic polymer chain have been extended and the contours of the three blocks could thereby be imaged separately.

A new K-region functionalized pyrene is presented which was used as a building block for the straightforward synthesis of hexaaryl[a,c,fg,j,l,op]tetracene via fourfold Stille coupling and subsequent cyclodehydrogenation. Electronic properties and crystal structures are provided and reveal a saddle conformation for the curved hexaarylated tetracenes.