Conjugated donor–acceptor substituted systems involving the 1,3-indandione-derived electron accepting moieties

Abstract

Conjugated donor–acceptor molecules are the focus of research owing to their unusual photo- and electro-physical properties. At the same time, several unusual features of these compounds are difficult to explain or predict. Here we present our results on the synthesis, X-ray structures and D-NMR spectra providing a deeper insight into the conjugation within the derivatives involving the 1,3-indandione-derived series of compounds with varying electron acceptor strength and conjugating bridge length. The X-ray structures show the presence of several intermolecular short contacts strongly affecting the molecular geometries. In solution, the coalescence temperatures corresponding to the rotation of the phenylamino moiety of all derivatives do not exceed 246 K indicating the unhindered rotation at room temperature. Using B3LYP/aug-cc-pVDZ, the calculated model chemistry barriers to rotation, dipole moments and first hyperpolarizabilities are within experimental error. We conclude that neglecting the electron donating properties of bridges themselves and internal rotation about the single bonds taking part in conjugation can result, for instance, in misinterpretation of their room temperature NMR spectra and overestimation of the computed molecular dipole moments by more than 5 D.