The work falls into catergories of organic and metal organic synthesis as well as into analysis of the electronic properties and application of the aromatic title compound 5,6:11,12-di-o-phenylenetetracene (DOPT) 1. The presented gram scale route to DOPT via its direct precursor molecule pseudorubrene 2 allows for the first time the investigation of their hitherto unknown reaction behavior. Pseudorubrene was converted into its Ag(I) salt together with fluorene and truxene. Moreover, DOPT was reduced with the entire alkaline metal series (Li, Na, K, Rb and Cs) as its respective solvent-shared and solvent-separated molecular ions. The rubidium and cesium complexes represent the first reported metal organic coordination compounds of DOPT, whereas isolation of the naked compounds of DOPT allowed for the first time an electronically uninfluenced view on the local electron distribution in isolated charged aromatic hydrocarbon species in the crystalline state.