Impact of the bromination of carbazole-based D-π-A organic dyes on their optical and electrochemical properties and visible-light-driven hydrogen evolution.

Brominated dyes, 2C-n (n = 1-5), 3C-4 and 4C-4, were prepared through bromination of three carbazole-based D-π-A dyes, 2C, 3C and 4C with N-bromosuccinimide (NBS). The detailed structures of the brominated dyes were confirmed by 1H NMR spectroscopy and mass spectrometry (MS). The introduction of the Br atom on the 1,8-positon of carbazole moieties led to blueshifted UV-vis and photoluminescence (PL) spectra, increased initial oxidation potentials and enlarged dihedral angles, indicating bromination enhanced non-planarity of the dye molecules. In the hydrogen production experiments, with the increase of the Br content in brominated dyes, the photocatalytic activity increased continuously (except 2C-1). The dye-sensitized Pt/TiO2, 2C-4@T, 3C-4@T and 4C-4@T, exhibited high hydrogen production efficiencies of 655.4, 877.9 and 905.6 μmol h-1 g-1, respectively, which were 4-6-fold higher than those of 2C@T, 3C@T and 4C@T. The enhanced performance of photocatalytic hydrogen evolution was attributed to decreased dye aggregation resulting from the highly non-planar molecular structures of the brominated dyes.