Torsional disorder and planarization dynamics: 9,10-bis(phenylethynyl)anthracene as a case study

Phys Chem Chem Phys. 2022 Nov 2;24(42):25979-25989. doi: 10.1039/d2cp03909e.

Abstract

Conjugated molecules with phenylethynyl building blocks are usually characterised by torsional disorder at room temperature. They are much more rigid in the electronic excited state due to conjugation. As a consequence, the electronic absorption and emission spectra do not present a mirror-image relationship. Here, we investigate how torsional disorder affects the excited state dynamics of 9,10-bis(phenylethynyl)anthracene in solvents of different viscosities and in polymers, using both stationary and ultrafast electronic spectroscopies. Temperature-dependent measurements reveal inhomogeneous broadening of the absorption spectrum at room temperature. This is confirmed by ultrafast spectroscopic measurements at different excitation wavelengths. Red-edge irradiation excites planar molecules that return to the ground state without significant structural dynamics. In this case, however, re-equilibration of the torsional disorder in the ground state can be observed. Higher-energy irradiation excites torsionally disordered molecules, which then planarise, leading to important spectral dynamics. The latter is found to occur partially via viscosity-independent inertial motion, whereas it is purely diffusive in the ground state. This dissimilarity is explained in terms of the steepness of the potential along the torsional coordinate.