Stimuli-Responsive Reversible Fluorescence Switching in a Crystalline Donor-Acceptor Mixture Film: Mixed Stack Charge-Transfer Emission versus Segregated Stack Monomer Emission.

ABSTRACT

We report on a molecularly tailored 11 donor-acceptor (D-A) charge-transfer (CT) cocrystal that manifests strongly red-shifted CT luminescence characteristics, as well as noteworthy reconfigurable self-assembling behaviors. A loosely packed molecular organization is obtained as a consequence of the noncentrosymmetric chemical structure of molecule A1, which gives rise to considerable free volume and weak intermolecular interactions. The stacking features of the CT complex result in an external stimuli-responsive molecular stacking reorganization between the mixed and demixed phases of the D-A pair. Accordingly, high-contrast fluorescence switching (red↔blue) is realized on the basis of the strong alternation of the electronic properties between the mixed and demixed phases. A combination of structural, spectroscopic, and computational studies reveal the underlying mechanism of this stimuli-responsive behavior.