Tuning of the Photovoltaic Parameters of Molecular Donors by Covalent Bridging

The synthesis of donor‐acceptor molecules involving triarylamines and dicyanovinyl blocks is described. Optical and electrochemical results show that rigidification of the acceptor part of the molecule by a covalent bridge leads to a ca. 0.20 eV increase of the band gap due to a parallel increase of the lowest unoccupied molecular orbital level. A preliminary evaluation of these compounds as donor materials in organic solar cells shows that although this structural modification reduces the light‐harvesting properties of the donor molecule, it nevertheless induces an increase of the efficiency of the resulting solar cells due to a simultaneous improvement of the open‐circuit voltage and fill factor.