Orthogonal 4,10 and 6,12 substitution of dibenzo[def,mno]chrysene polycyclic aromatic small moleculesElectronic supplementary information (ESI) available. CCDC 1526927 and 1526928. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7tc02528a

A series of new polycyclic aromatic hydrocarbon compounds based on (4,10-disubstituted-dibenzo[def,mno]chrysene-6,12-dione) and 4,10 di-substituted 6,12-bis(triisopropylsilylethynyl)dibenzo[def,mno]chrysene are reported with tunable electronic properties through varied molecular architecture. Starting with an inexpensive commercially available textile dye known as Vat Orange #3, (4,10-dibromo-dibenzo[def,mno] chrysene-6,12-dione) we extended the conjugation at the 4- and 10-positions by the attachment of both electron rich and deficient hexylvinylphthalimide, thiophene, hexylthiophene, triphenylamine, and hexylbithiophene aromatic groups, and studied the resultant optoelectronic properties. By applying various synthetic metal-catalyzed reactions, soluble dibenzo[def,mno]chrysene and dibenzo[def,mno]chrysene-6,12-dione derivatives were achieved with optical edge band gaps between 2.30 eV and 1.65 eV. Polycyclic aromatic hydrocarbon compounds based on 4,10 and 6,12-functionalized dibenzo[def,mno]chrysene are reported with tunable electronic properties through varied molecular architecture.