Phenylethynylanthracene based push–pull molecular systems: tuning the photophysics through para-substituents on the phenyl ring

Organic push–pull molecules contain donor and acceptor moieties connected via π-linkages through which intramolecular electron charge transfer (ICT) can occur in the ground and excited states; giving these molecules interesting photophysical properties. The molecules chosen in this work are some basic phenylethynylanthracene derivatives to show that with just a change of substituents this class of small molecules can show dramatic changes in their photophysical properties. The emission properties and ICT abilities of these molecules are compared with regards to various electron donating and withdrawing substituents. Substituents such as cyano and methoxycarbonyl groups do not induce any ICT character whereas substituents like aldehyde, N,N-dimethylamino and nitro groups cause appreciable ICT character in this class of molecules and their emission spectra extend almost throughout the whole visible region. The comparative ICT character was correlated with the results of electron density difference calculations. Computational studies show that the molecules are planar in their ground as well as excited states; except the nitro group containing molecule, which has an orthogonally twisted structure in the excited state. The emission properties of this molecule led to its inclusion into a class of nitroaromatics which shows maximum emission intensity in moderately polar solvents and the emission is quenched drastically by either decreasing or increasing solvent polarity. Fluorescence anisotropy studies show very good sensitivity of these compounds towards microviscosity of their immediate molecular environment. A white light emitting (WLE) gel was prepared using 4-(anthracen-9-ylethynyl)benzonitrile (AnPCN) and 4-(anthracen-9-ylethynyl)-N,N-dimethylaniline (AnPNMe2) by taking polyvinyl alcohol (PVA) as the gelator and the resulting gel exhibited very good CIE (0.31, 0.33) with CCT (6598 K) and CRI (87). As an example, the use of the gel was also demonstrated by applying it to a commercial UV LED which showed satisfactory results. AnPNMe2 was used to sense polar solvent vapors in TLC plates and Whatman paper due to its good solvatochromic behavior.