Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines
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A facile synthesis of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridine derivatives is reported which is based on POCl 3 -mediated cyclodehydration followed by double Suzuki–Miyaura cross-coupling. The absorption and fluorescence properties of the obtained products were investigated and their HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. Besides, density functional theory calculations were carried out for further exploration of their electronic properties.Keywords:
HOMO/LUMO
Suzuki reaction
Abstract The ground‐state structure and frontier molecular orbital of D‐π‐A organic dyes, CFT1A, CFT2A, and CFT1PA were theoretically investigated using density functional theory (DFT) on B3LYP functional with 6‐31G(d,p) basis set. The vertical excitation energies and absorption spectra were obtained using time‐dependent DFT (TD‐DFT). The adsorptions of these dyes on TiO 2 anatase (101) were carried out by using a 38[TiO 2 ] cluster model using Perdew–Burke–Ernzerhof functional with the double numerical basis set with polarization (DNP). The results showed that the introduction of thiophene–thiophene unit (T–T) as conjugated spacer in CFT2A could affect the performance of intramolecular charge transfer significantly due to the inter‐ring torsion of T–T being decreased compared with phenylene–phenylene (P–P) spacer of CFP2A in the researhcers' previous report. It was also found that increasing the number of π‐conjugated unit gradually enhanced charge separation between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of these dyes, leading to a high‐efficiency photocurrent generation. The HOMO–LUMO energy gaps were calculated to be 2.51, 2.37, and 2.50 eV for CFT1A, CFT2A, and CFT1PA respectively. Moreover, the calculated adsorption energies of these dyes on TiO 2 cluster were ∼14 kcal/mol, implying that these dyes strongly bind to TiO 2 surface. Furthermore, the electronic HOMO and LUMO shapes of all dye–TiO 2 complexes exhibited injection mechanism of electron via intermolecular charge‐transfer transition. © 2012 Wiley Periodicals, Inc.
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Carbazole
Mulliken population analysis
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Effect of inorg anic additives on the cyclic voltammetry curves of lead negative for leadacid ba ttery were studied by means of cyclic voltammetry method.The results show that there is only a pair of electricity peaks in the cyclic voltammetry curve of the lead cathode in 4.30 mol/L H2SO4 solution, and the position of deoxidizationcurrent peak is similar to the H2gassing potential. Except for CdSO4, the other additives do not change the shape of cyclic voltammetry curve and they cause the position of electricity peaks have little change. However, CdSO4 additive makes a new electricity peak at -1.050 V in the cyclic voltammetry curve.
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The operation of organic light emitting diodes (OLEDs) is governed by a range of material parameters, such as frontier orbital energy levels, charge carrier mobility and excitonic rate parameters. In state-of-the art numerical simulations of OLED devices, more than 30 parameters must be considered to describe the behavior of a multilayer device. Independent measurement techniques to reliably determine each material parameter individually are therefore highly desirable. While several techniques have been established in the OLED community to determine some of them, the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energy levels are not measured or reported on a regular basis, despite their significant influence on device performance. In this work, we show how cyclic voltammetry in solution can be used as a simple technique to measure the HOMO and LUMO energy levels of organic semiconductors. This easily performed experiment allows a fairly accurate estimation of the energy levels of the layers in a device stack. Cyclic voltammetry measurements of four typical OLED materials in solution are presented and their analysis is described in detail to encourage more such measurements in future OLED studies. Four distinctly different voltammograms were obtained, ranging from relatively ideal reversible behavior to a very non-ideal behavior, lacking electrochemical reverse reactions. Two methods for extracting the HOMO and LUMO energy levels from cyclic voltammetry are discussed and compared. The measured HOMO and LUMO levels compare well with reported values measured on thin films, showing that cyclic voltammetry in solution provides a viable means to determine this important, yet underinvestigated material property.
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Highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) tuning is an important consideration in the development of organic‐based semiconducting materials. A study of the specific effects and overall trends for the HOMO–LUMO tuning of a diverse series of 9‐fluorenones by means of extended conjugation and substituent effects is described. Trends were explored in a range of compounds, beginning with structures having highly electron‐withdrawing substituents and progressing to structures having highly electron‐donating substituents. Compounds with an incremental increase in conjugation were also examined. Electrochemical and optical measurements were used to calculate the HOMO–LUMO levels and HOMO–LUMO bandgap (HLG) for each structure. Results from both methods were compared and correlated with the differences in molecular structure. Increasing the electron‐donating character of the substituents was observed to decrease the HLG and increase the energy levels of the HOMO and the LUMO, whereas an increase in the electron‐withdrawing character produced the opposite results. Increasing conjugation decreased the HLG, increased the HOMO energy level, but decreased the LUMO energy level. Spectroscopic evidence of substituent influence on the carbonyl suggests that substituents directly impact the HLG by influencing the availability of nonbonding electrons within the carbonyl, which impacts the probability of an nπ* transition. The data presented not only elaborate on the HOMO–LUMO tuning of 9‐fluorenone systems but also enable the consideration of 9‐fluorenones as analogous models for HOMO–LUMO tuning in other more complex polyaromatic systems such as bifluorenylidenes. These trends may provide insight into developing materials with specifically tuned HLGs and HOMO–LUMO levels for a variety of applications. Copyright © 2011 John Wiley & Sons, Ltd.
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