Highly Photoactive Polythiophenes Obtained by Electrochemical Synthesis from Bipyridine-Containing Terthiophenes

According to numerous previous reports, a Z-scheme with two photon absorbers is the most promising strategy to achieve artificial photosynthesis, but in addition to two efficient catalysts — one for oxygen evolution, the other for CO2 reduction — two different and complementary semiconducting sensitizers are required. Here we present the synthesis of two bipyridine-functionalized terthiophenes, which can be electropolymerized to give photoactive p-type semiconductors the capability to perform as photocathode in photoelectrochemical cells for water photosplitting or artificial photosynthesis. Indeed the bipyridine moiety in their structure allows the binding of transition metal carbonyl complexes employed in CO2 reduction, and their band-gap is suitable for the coupling with wide band-gap semiconductors, which have already found application as photoanodes. Finally, they are characterized by photogenerated charge carrier density between 1.1 and 1.4 × 1019 cm−3, with first-order recombination constant of 0.7–1.8 × 10−2 s−1. These figures are of the same order of magnitude of their inorganic counterparts and would therefore guarantee photoconductivity of the device and the activation of the organometallic catalysts with which they should be coupled to function as photocathodes for CO2 reduction