Investigation of Weak Noncovalent Interactions Directed by the Amino Substituent of Pyrido- and Pyrimido-[1,2-a]benzimidazole-8,9-diones.

Quinones are small redox-active molecules that are able to form intra- and intermolecular interactions both in the solid state and in solution. On the basis of 6-amino-substituted pyrido- and pyrimido-[1,2-a]benzimidazole-8,9-diones, weak interactions were investigated by single-crystal X-ray and 1H NMR spectroscopy methods. Crystallization of quinone derivatives containing a -NH-CH2- fragment led to the formation of both chiral and achiral crystals. The presence of two forms with (endo form) and without (exo form) an intramolecular hydrogen bond was experimentally detected by X-ray crystallography analysis and variable-temperature (VT) 1H NMR experiments in the cases of isopentylamino- and benzylamino-substituted derivatives. Interestingly, the exo form dominates both in the solid state and in solution.

Emission Enhancement by Intramolecular Stacking between Heteroleptic Iridium(III) Complex and Flexibly Bridged Aromatic Pendant Group.

Phosphorescent iridium(III) complexes suffer from a strong aggregation quenching, limiting their use in solution-processed or crystalline organic light-emitting diodes. Here we report how an intramolecular stacking between a flexibly bridged bulky aromatic pendant group and the core of nonionic heteroleptic complex can be exploited to minimize the negative effects of this drawback. The stacked conformation provides a rigid sterical shielding of the polar molecular surface, improving photoluminescence quantum yield of the complex both in solution and crystalline state.

Unusual response to environmental polarity in a nonlinear-optical benzylidene-type chromophore containing a 1,3-bis(dicyanomethylidene)indane acceptor fragment.

One of the strongest known electron-accepting fragments used in the synthesis of organic dyes for applications in nonlinear optics (NLO) is 1,3-bis(dicyanomethylidene)indane (BDMI). By studying a benzylidene-type push-pull chromophore bearing a 5-carboxy-BDMI electron-acceptor and 4-(dimethylamino)aniline donor fragment, we demonstrate that this class of compounds can show unusual response to the polarity of the surrounding medium. The combined results of UV-Vis absorption spectrometry, NMR experiments and computational modeling indicate that the studied compound undergoes a geometrical transformation that involves an increase in the torsion angle ω between the aniline and indane ring systems with the rise of the polarity of the surrounding medium. This process is partly facilitated by an increased rotational freedom around ω in more polar solvents, as detected experimentally by NMR and predicted by calculations. Regarding the practical application aspects, computations predict that the solvent-polarity-induced increase of torsion ω would lead to a notable decrease in the first hyperpolarizability (ß) value. This was detected experimentally, as hyper-Rayleigh scattering (HRS) data showed a drop in the compound's NLO activity from ßHRS(532) = 513 × 10-30 esu in toluene to ßHRS(532) = 249 × 10-30 esu in acetonitrile. This places limitations on the NLO applications of the studied compound and its structural analogues, as the surrounding medium (solvent of polymer matrix) with the lowest possible polarity needs to be used to maximize their NLO efficiency.