Novel D-A-π-A1 Type Organic Sensitizers from 4,7-Dibromobenzo[d][1,2,3]thiadiazole and Indoline Donors for Dye-Sensitized Solar Cells

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-06, Vol.27 (13), p.4197
• Main Authors: Gudim, Nikita S., Knyazeva, Ekaterina A., Mikhalchenko, Ludmila V., Mikhailov, Maksim S., Zhang, Lu, Robertson, Neil, Rakitin, Oleg A.
• Format: Article
• Language: English
• Subjects: Acids; Benzene; benzo[d][1,2,3]thiadiazole; Carbazole; Carbazoles; Carbon; Chemical reactions; Cross coupling; Cyclohexane; Cyclopentane; D-A-π-A1 dyes; Dye-sensitized solar cells; Dyes; electrochemical properties; Energy resources; Isomers; Magnetic resonance spectroscopy; Molecular orbitals; Molecular structure; NMR; NMR spectroscopy; Nuclear magnetic resonance; optical properties; Photovoltaics; Power efficiency; Solar cells; Solvents; Spectrum analysis; Suzuki cross-coupling reaction; Thiadiazoles; Voltammetry; X-ray diffraction
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27134197

Two novel D-A-π-A1 metal-free organic dyes of the KEA series containing benzo[d][1,2,3]thiadiazole (isoBT) internal acceptor, indoline donors fused with cyclopentane or cyclohexane rings (D), a thiophene as a π-spacer, and a cyanoacrylate as an anchor part were synthesized. Monoarylation of 4,7-dibromobenzo[d][1,2,3]thiadiazole by Suzuki-Miyamura cross-coupling reaction showed that in the case of indoline and carbazole donors, the reaction was non-selective, i.e., two monosubstituted derivatives were isolated in each case, whereas only one mono-isomer was formed with phenyl- and 2-thienylboronic acids. This was explained by the fact that heterocyclic indoline and carbazole fragments are much stronger donor groups compared to thiophene and benzene, as confirmed by cyclic voltammetry measurements and calculation of HOMO energies of indoline, carbazole, thiophene and benzene molecules. The structure of monoaryl(hetaryl) derivatives was strictly proven by NMR spectroscopy and X-ray diffraction. The optical and photovoltaic properties observed for the KEA dyes showed that these compounds are promising for the creation of solar cells. A comparison with symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 showed that the asymmetric nature of benzo[d][1,2,3]thiadiazole KEA dyes leads to a hypsochromic shift of the ICT band in comparison with the corresponding benzo[c][1,2,5]thiadiazole isomers. KEA dyes have a narrow HOMO-LUMO gap of 1.5–1.6 eV. Amongst these dyes, KEA321 recorded the best power efficiency (PCE), i.e., 5.17%, which is superior to the corresponding symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 (5.07 and 4.90%).