Synthesis, photophysics and two-photon absorption of imidazole-centred tripodal chromophores

Abstract

Tripodal push–pull chromophores with D–(π–A)₃ arrangement were synthesized using 1-methyl-2,4,5-triphenyl-1H-imidazole as a central electron donor, and their thermal, electrochemical, photophysical and non-linear optical properties were studied and corroborated with quantum-chemical calculations. Their facile synthesis involved Suzuki–Miyaura and Knoevenagel reactions, allowing the installation of various peripheral electron acceptors such as formyl, cyano, ester, trifluoromethyl and more complex moieties such as malonic/acetic acid derivatives, indan-1,3-dione and rhodanine. All phenyl rings appended at the central imidazole core were more or less twisted depending on the peripheral substitution. Although imidazole undergoes reversible one-electron oxidation, peripheral acceptors are reduced irreversibly in a multi-electron process. This behaviour is further seen as a variation of the LUMO, while the HOMO remained almost unaltered across the whole series. TD-DFT calculations revealed centrifugal charge transfer from the central imidazole to all C2, C4 and C5 branches occupied by the LUMO, LUMO+1 and LUMO+2. The HOMO–LUMO gap is tuneable within the range of 3.55–2.31 eV, while the longest-wavelength absorption/emission maxima were found within the broad range of 304–448/393–612 nm. Although the absorption spectra are solvent-independent, the emission depends strongly on the solvent polarity and the electron-withdrawing power of the peripheral acceptors. Extended chromophores with complex electron acceptors were investigated as two-photon absorbers, revealing relatively good cross-section values of up to 521 GM and a figure-of-merit (Φ_F × δ_2PA) of around 190 GM.