  Starphenes are attractive compounds due to their characteristic
physicochemical properties that are inherited from acenes, making them
interesting compounds for organic electronics and optics. However, the
instability and low solubility of larger starphene homologs make their
synthesis extremely challenging. Herein, we present a new strategy leading to
pristine [16]starphene in preparative scale. Our approach is based on a
synthesis of a carbonyl-protected starphene precursor that is thermally
converted in a solid-state form to the neat [16]starphene, which is then
characterised with a variety of analytical methods, such as 13C CP-MAS NMR,
TGA, MS MALDI, UV-Vis and FTIR spectroscopy. Furthermore, high-resolution STM
experiments unambiguously confirm its expected structure and reveal a moderate
electronic delocalisation between the pentacene arms. Nucleus-independent
chemical shifts NICS(1) are also calculated to survey its aromatic character.
