At the outset we focused on the preparation of the DPP 1 containing bromine atoms on the fluorene unit, which was achieved following the previously reported literature procedure (Scheme 1). The pigment was then modified by introducing an arylalkyne substituent. In order to enable the solubilization of the starting material in solvents commonly used in organic synthesis, the nitrogen atoms of the lactam core were protected with tert-butoxycarbonyl groups (Boc). The formed bis-Boc-DPP 2 was then subjected to Sonogashira coupling with 4-tert-butylphenylacetylene which resulted in the formation of DPP 3. It is important to note that the reaction must be carried out at a temperature equal or below 80 ºC, otherwise it leads to a mixture of products due to partial deprotection of the Boc groups of the substrate. Finally, the product of the double Sonogashira reaction i.e. DPP 3 was deprotected by adding TFA to the pigment solution in methylene chloride. This generated free DPP 4 in the quantitative reaction yield (Scheme 1). Subsequently, N-arylation of DPP 4 was carried out with electronpoor aryl fluorides namely methyl 3-bromo-2-fluoro-5-nitrobenzoate and methyl 3-bromo-4-fluoro-5-nitrobenzoate, in the presence of potassium carbonate in NMP (Scheme 1). The reaction was completed after 4 days, yielding 5 and 6, respectively. The N-arylation of DPP 4 proceeded much slower compared to the previously described DPP bearing benzofuran units, where the reaction was completed after a few hours. 6a In the next step, both 5 and 6 were subjected to Pd(PPh3)4 in order to perform intramolecular, direct arylation in our systems. As a result we obtained good yields of two π-expandable products: 7 and 8, both possessing 12 fused rings. The reaction was carried out overnight in dry toluene at 115 °C. Both target pigments are soluble in chlorinated and aromatic solvents, which enabled their identification using 1 H NMR and 13 C NMR spectroscopy. Scheme 1. The preparation of DPPs 7 and 8.