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 via oCVD and on the optoelectronic properties of the resulting thin films. We found that the nature of the chelated cation strongly affects the intermolecular coupling efficiency, as well as the occurrence of side reactions such as chlorination, intramolecular cyclization, demetallation/re-metalation, and oxidation of the porphyrin core. Moreover, we discussed the influence of the above-mentioned reactions on the optoelectronic properties of the fused metalloporphyrin coatings, in view of their potential application in photo-electrocatalytic systems. This study paves the way toward the engineering and future implementation of porphyrin-based systems for clean and efficient solar fuel production.