Electronic and energy level engineering of directly fused porphyrin-conjugated polymers – impact of the central metal cation

The integration of porphyrins and their derivatives in functional devices for solar-assisted fuel production is both highly attractive and challenging due to the difficulties in processing them. This limitation is overcome in the gas-phase approach, particularly by oxidative chemical vapor deposition (oCVD), leading to the simultaneous synthesis and deposition of conjugated porphyrin coatings. We have investigated the impact of the metal cation of 5,15-diphenyl metalloporphyrins (MDPP; M = Co, Cu, Mg, Zn, Pd, Pt, Ag, Ru, Ag, and FeCl) on the dehydrogenative coupling reaction leading to fused-metalloporphyrin thin films