Structural effects on the photoelectrochemical properties of new push-pull dyes based on vinazene acceptor triphenylamine donor

• Were synthesized novel dyes based on vinazene acceptor and triphenylamine donor.
• The synthesized dyes exhibit push-pull character and lowest charge-transfer excited state.
• Calculated electronic properties were consistent with experimental data for the dyes reported.
• The experiments confirming the feasibility of photoinduced electrons in TiO2 conduction band and regeneration by I−/I3−.
• The efficiency also depends on conformation and number of anchoring CN groups to mesoporous TiO2 surface.

The push-pull behavior of novel dyes, based on vinazene electron-acceptor groups linked to arrays of triphenylamine (TPA) electron-donor group, was studied by electronic absorption and emission spectroscopy, as well as by cyclic voltammetry. The most stable ground state structure and their electronic properties were modeled by density functional theory (DFT) calculations using the B3LYP functional and 6-31G++ basis set, whereas the electronic properties in the excited states were calculated by TD-DFT, under the same functional and basis set, using SCF and PCM methods. The theoretical calculations matched well with experimental data, showing that λmax of the lowest energy absorption band can be assigned to an intramolecular charge transfer transition. In fact, the HOMO and LUMO are respectively localized on the TPA donor and the dicyanomethylene acceptor moiety confirming a remarkable push-pull character. Photoelectrochemical cells parameters were correlated with dyes structural properties showing to be consistent with the anchoring through the nitrogen atoms of CN groups. The nature of the donor-acceptor groups, conformation and number of anchoring CN groups (2 seems to be the best) strongly influenced the overall efficiency of dye sensitized solar cells.

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