Unexpected multiple activated steps in the excited state decay of some bis(phenylethynyl)-fluorenes and -anthracenes

The temperature effect on the photophysical parameters of four acetylene-derivatives [bis(phenylethynyl)-anthracenes and -fluorenes with substituents of different electron acceptor efficiencies] has been investigated by absorption and emission spectroscopy, using stationary and pulsed (ns/fs resolution) techniques. The nature of the central nucleus (anthracene or fluorene) and the peripheral electron-withdrawing group (nitro or formyl) strongly affect the deactivation of the excited states of these push–pull molecules. In some cases the study evidenced an interesting role of two activated steps in the deactivation of the excited singlet state, namely an activated inter-system crossing to an upper triplet state of n,π* nature (previously hypothesized on the basis of TD-DFT calculations) and a sort of activated internal conversion, discussed also on the basis of maximum entropy method analysis of the fluorescence decay data. Nicely, an efficient ISC was found for the fluorene-derivatives where small energy gaps between S1 (π,π*) and Tn (n,π*) states had been calculated while no activated ISC was evidenced in the case of anthryl-derivatives where higher S1–Tn energy gaps are expected. A peculiar temperature effect for a fluorene-derivative was pointed out and also explained on the basis of quantum-mechanical calculations at the DFT level taking into account the solvation effects by means of the conductor-like polarizable continuum model CPCM. The presence of dual emission, at first evidenced by a shoulder in the emission spectrum of the fluorene-derivative featuring a peripheral formyl group in dichloromethane at low temperatures, was nicely confirmed by femtosecond up-conversion measurements at room temperature.