Full Length ArticleSynthesis, DFT studies and photovoltaic characteristics of 2-amino-N-cyclohexyl-5-oxo-5H-chromeno[2,3-b]pyridine-3-carboxamide (ACCP)
Graphical abstract
Introduction
Chromone derivatives showed variable biological activities including anticancer [1], [2], antitumor [3], neuroprotective [4], HIV-inhibitory [5], antimicrobial [6], and antioxidant [7], [8]. Introducing an electron-withdrawing cyano group in the chromone nucleus especially at the 3-position of the changes remarkably the reactivity of the γ-pyrone ring with respect to nucleophiles, providing a wide synthetic potential of chromone-3-carbonitriles [9], [10], [11], [12], [13], [14]. Chromone-3-carbonitriles acquire the ability to undergo a nucleophilic 1,4-attack followed by additional transformations related to γ-pyrone ring opening and heterocyclizations at the C-4 atom or at the cyano group. The DFT-theoretical calculation can be used for the investigation of the optimized geometries of the synthesized compound 2-amino-N-cyclohexyl-5-oxo-5H-chromeno[2,3-b]pyridine-3-carboxamide (ACCP). Also, study the dipole moment, atomic charge, FT-IR, equilibrium geometries, harmonic vibrational frequencies, thermo-chemical parameters, energetic of the molecule and molecular electrostatic potential contours (MEP, ESP, ED). In addition to the time dependant density functional theory (TD-DFT) [15], one can investigate the effect of solvent polarity on the observed spectra and hence, predict some of the main physical characteristics and assignment the predictable electronic transitions.
Kupcewicz et al. [16] have synthesized a new fluorescent Zn(II) complex with 7-amino-2-methylchromone and showed a good solubility for the prepared complex in organic solvents. They also recorded the applicability of this complex for potential application in the blue organic light-emitting device due its strong bright-blue emission fluoresces under UV irradiation in both solid state and solution.
Ibrahim et al. [17] have recorded a maximum photosensitivity of the device based 10-chloro-6H,8H-dichromeno[2,3-b:3′,4′-e]pyridine-6,8-dione (CDPD) thin film under illumination effect of 60 mW/cm2 and bias voltage of 1.25 V. In addition, they investigated the phototransient current characteristics of the presented device under different light intensity illuminations for light photodetector application.
The aim of the present work is to study the chemical transformations of chromone-3-carbonitrile (1) towards 2-cyano-N-cyclohexylacetamide as cyclic active methylene nucleophile hoping to construct a new derivative of heteroannulated chromones. Moreover, the structure was characterized by various spectroscopic analysis. Moreover, the quantum chemical calculations were done by using DFT analysis. Furthermore, the morphological characteristics of the prepared samples and its particle size determination were achieved by scanning electron microscopy (SEM) and particle size analyzer, respectively. The spectroscopic characteristics were studied to obtain the main optical absorption and dispersion parameters. Finally, the ACCP thin film-based heterojunction device application was introduced in dark and under various illumination intensity in the range 20–100 mW/cm2.
Section snippets
Preparation and molecular structural characterizations of 2-Amino-N-cyclohexyl-5-oxo-5H-chromeno[2,3-b]pyridine-3-carboxamide (ACCP)
A mixture of chromone-3-carbonitrile (1) (0.86 g, 5 mmol) and 2-cyano-N-cyclohexylacetamide (0.83 g, 5 mmol) in absolute ethanol (30 mL) containing DBU (0.1 mL) was heated under reflux for 15 min. The pale yellow crystals obtained during heating were filtered and recrystallized from DMF/EtOH to give ACCP as a pale yellow crystals, mp 310–311 °C, yield (1.42 g, 85%). IR (KBr, cm−1): 3437, 3336, 3141 (NH2, NH), 2930, 2854 (CHaliph.), 1630 (COγ-pyrone and COamide), 1523 (CN and CC). 1H NMR (DMSO,
Molecular structure and reaction confirmation
In the current study, the chemical reactivity of chromone-3-carbonitrile (1) was studied towards 2-cyano-N-cyclohexylacetamide as a cyclic active methylene nitrile hoping to construct a new derivative of heteroannulated chromones and study its optical properties.
Thus, treatment of chromone-3-carbonitrile (1) with 2-cyano-N-cyclohexylacetamidein boiling ethanol containing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a basic catalyst afforded 2-amino-N-cyclohexyl-5-oxo-5H-chromeno[2,3-b
Conclusion
In conclusion, 2-amino-N-cyclohexyl-5-oxo-5H-chromeno[2,3-b]pyridine-3-carboxamide (ACCP) was efficiently synthesized from base catalyzed ring opening and ring closure (RORC) reaction of chromone-3-carbonitrile (1) with 2-cyano-N-cyclohexyl acetamide. The most stable geometry at B3LYB/6-311G (p,d) level of ACCP was determined. The electronic absorption spectra of ACCP were carried out by TD-DFT calculation. The (π-π*) transitions assigned in all the observed bands can be reflected from their
Acknowledgment
The authors are grateful to the Physics and Chemistry Departments, Faculty of Education, Ain Shams University, and Electronics Materials Dep. Advanced Technology& New Materials Research Inst., City of Scientific Research & Technological Applications (SRTA-City), New Borg El-Arab City, Alexandria, Egypt for supporting the achievement of this work.
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