Z/E-Isomerism of 3-[4-(dimethylamino)phenyl]-2-(2,4,6-tribromophenyl)acrylonitrile: crystal structures and secondary intermolecular interactions.

The Z and E isomers of 3-[4-(dimethylamino)phenyl]-2-(2,4,6-tribromophenyl)acrylonitrile, C17H13Br3N2, (1), were obtained simultaneously by a Knoevenagel condensation between 4-(dimethylamino)benzaldehyde and 2-(2,4,6-tribromophenyl)acetonitrile, and were investigated by X-ray diffraction and density functional theory (DFT) quantum-chemical calculations. The (Z)-(1) isomer is monoclinic (space group P21/n, Z' = 1), whereas the (E)-(1) isomer is triclinic (space group P-1, Z' = 2). The two crystallographically-independent molecules of (E)-(1) adopt similar geometries. The corresponding bond lengths and angles in the two isomers of (1) are very similar. The difference in the calculated total energies of isolated molecules of (Z)-(1) and (E)-(1) with DFT-optimized geometries is ∼4.47 kJ mol-1, with the minimum value corresponding to the Z isomer. The crystal structure of (Z)-(1) reveals strong intermolecular nonvalent Br...N [3.100 (2) and 3.216 (3) Å] interactions which link the molecules into layers parallel to (10-1). In contrast, molecules of (E)-(1) in the crystal are bound to each other by strong nonvalent Br...Br [3.5556 (10) Å] and weak Br...N [3.433 (4) Å] interactions, forming chains propagating along [110]. The crystal packing of (Z)-(1) is denser than that of (E)-(1), implying that the crystal structure realized for (Z)-(1) is more stable than that for (E)-(1).

Characterization of ion profiles in light-emitting electrochemical cells by secondary ion mass spectrometry.

Ion profiles in polymer light-emitting electrochemical cells are known to significantly affect performance and stability, but are not easily measured. Here, secondary ion mass spectrometry is used to investigate ion profiles in both dynamic and chemically fixed junction devices. Results indicate lower reversibility of dynamic junctions and a more significant time delay for ion redistribution than previously expected, but confirm the complete immobilization of ions in chemically fixed junction devices. When compared with prior studies analyzing the electric field profiles in similar devices, these results help to elucidate the roles of ion distribution and electrochemical doping in LECs.

Precise color tuning via hybrid light-emitting electrochemical cells.

We report color-tunable light-emitting devices employing CdSe/ZnS quantum dots (QDs) blended into a polymer light-emitting electrochemical cell (LEC) architecture. This novel structure circumvents the charge-tunneling barrier of QDs to achieve bright, uniform, and highly voltage-independent electroluminescence, with nearly all emission generated by the QDs. By blending varying ratios of two QD materials that emit at different wavelengths, we demonstrate precise color control in a single layer device structure.