Efficient OLEDs Fabricated by Solution Process Based on Carbazole and Thienopyrrolediones Derivatives.

Four low molecular weight compounds-three of them new, two of them with carbazole (Cz) as functional group and the other two with thienopyrroledione (TPD) group-were used as emitting materials in organic light emitting diodes (OLEDs). Devices were fabricated with the configuration ITO/PEDOT:PSS/emitting material/LiF/Al. The hole injector layer (HIL) and the emitting sheet were deposited by spin coating; LiF and Al were thermally evaporated. OLEDs based on carbazole derivatives show luminances up to 4130 cd/m², large current efficiencies about 20 cd/A and, cautiously, a very impressive External Quantum Efficiency (EQE) up to 9.5%, with electroluminescence peaks located around 490 nm (greenish blue region). Whereas, devices manufactured with TPD derivatives, present luminance up to 1729 cd/m², current efficiencies about 4.5 cd/A and EQE of 1.5%. These results are very competitive regarding previous reported materials/devices.

Small Molecules Derived from Thieno[3,4-c]pyrrole-4,6-dione (TPD) and Their Use in Solution Processed Organic Solar Cells.

In this work, microwave synthesis, chemical, optical and electrochemical characterization of three small organic molecules, TPA-TPD, TPA-PT-TPD and TPA-TT-TPD with donor-acceptor structure and their use in organic photovoltaic cells are reported. For the synthesis, 5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione was used as electron withdrawing fragment while the triphenylamine was used as electron donating fragment. Molecular electronic geometry and electronic distribution density were established by density functional theory (DFT) calculations and confirmed by optical and chemical characterization. These molecules were employed as electron-donors in the active layer for manufacturing bulk heterojunction organic solar cells, where [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) was used as electron-acceptor. As cathode, Field's metal (FM), an eutectic alloy (Bi/In/Sn: 32.5%, 51%, and 16.5%, respectively) with a melting point above 62 °C, was easily deposited by drop casting under vacuum-free process and at air atmosphere. Prepared devices based on TPA-TPD:PC71BM (1:4 w/w ratio) presented a large VOC = 0.97 V, with JSC = 7.9 mA/cm², a FF = 0.34, then, a power conversion efficiency (PCE) of 2.6%.

Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction.

This paper reports the synthesis of a series of piperidones 1-8 by the Mannich reaction and analysis of their structures and conformations in solution by NMR and mass spectrometry. The six-membered rings in 2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-ones, compounds 1 and 2, adopt a chair-boat conformation, while those in 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ones, compounds 3-8, adopt a chair-chair conformation because of stereoelectronic effects. These stereoelectronic effects were analyzed by the (1) J C-H coupling constants, which were measured in the (13)C satellites of the (1)H NMR spectra obtained with the hetero-dqf pulse sequence. In the solid state, these stereoelectronic effects were investigated by measurement of X-ray diffraction data, the molecular geometry (torsional bond angles and bond distances), and inter- and intramolecular interactions, and by natural bond orbital analysis, which was performed using density functional theory at the ωB97XD/6311++G(d,p) level. We found that one of the main factors influencing the conformational stability of 3-8 is the interaction between the lone-pair electrons of nitrogen and the antibonding sigma orbital of C(7)-Heq (nN→σ*C-H(7)eq), a type of hyperconjugative interaction.

NMR structural study of the prototropic equilibrium in solution of Schiff bases as model compounds.

An NMR titration method has been used to simultaneously measure the acid dissociation constant (pKa) and the intramolecular NHO prototropic constant ΔKNHO on a set of Schiff bases. The model compounds were synthesized from benzylamine and substituted ortho-hydroxyaldehydes, appropriately substituted with electron-donating and electron-withdrawing groups to modulate the acidity of the intramolecular NHO hydrogen bond. The structure in solution was established by 1H-, 13C- and 15N-NMR spectroscopy. The physicochemical parameters of the intramolecular NHO hydrogen bond (pKa, ΔKNHO and ΔΔG°) were obtained from 1H-NMR titration data and pH measurements. The Henderson-Hasselbalch data analysis indicated that the systems are weakly acidic, and the predominant NHO equilibrium was established using Polster-Lachmann δ-diagram analysis and Perrin model data linearization.

(E)-4-Hy-droxy-2-{[(2-phenyl-eth-yl)iminium-yl]meth-yl}phenolate.

The title Schiff base compound, C(15)H(15)NO(2), crystallized as the iminium-phenolate zwitterion. The H atom is localized on the imine N atom, forming a strong intra-molecular hydrogen bond with the phenolate O atom, and giving rise to an S(6) ring motif. The mol-ecule has an E conformation about the C=N bond. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming chains propagating along [010]. There are also C-H⋯O inter-actions present.

Relative acidities and structure analysis of cis and trans isomers of 1,5-oxazaspiro[5.5] undecane derivatives by multinuclear magnetic resonance.

The relative acidities of the cis and trans isomers of a series of 1,5-oxazaspiro[5.5]undecane derivatives were determined by measuring DeltapK in acid-base titrations followed by (1)H NMR. Relative structural stabilities were determined by measuring substituent chemical shift and gamma-gauche effects in (13)C, (15)N, and (17)O NMR. Crystallographic characterization of a model spiro[5.5]undecane is presented to support the basicity in solid state.