Synthesis, Characterization, Density Functional Theory Analyses And Nonlinear Optical Properties Of New Chalcone Derivatives

A series of new anthracenyl chalcone compounds were successfully synthesized using Claisen Schmidt condensation method. These anthracenyl chalcone derivatives structures have been determined and refined using X-ray single crystal diffraction data and optimized at the ground state using density functional theory (DFT) method. The compounds were then characterized by using FTIR, NMR and UV-Vis methods. The presence of functional group and the number of carbon and proton in the molecular structure are confirmed by FTIR and NMR spectroscopy, respectively. The UV-Vis spectrum shows all chalcones have higher maximum wavelength (386-422 nm) and good transparency window for optical application. The experimental spectroscopic data were compared with the theoretical DFT spectra, where the values show good agreement. The existences of intermolecular hydrogen bonds in all compounds play important roles in their packing pattern and NLO properties. All the compounds show a good HOMO-LUMO energy gap values which indicate potential for optoelectronic applications. The molecular electrostatic potential (MEP) identifies the positive, negative and neutral electrostatic potential regions of the molecules. The difference substituents to the anthracenyl chalcone affect the dipole moments and NLO response of the compounds. The nonlinear absorption coefficient (β) and nonlinear refractive index (n2) have been evaluated from the open aperture and closed aperture Z-scan. Based on the measured nonlinear susceptibility χ3, all structures offers great potential in applications such as optical switching and optical limiting applications

Third Order Optical Nonlinearity Of Linear Fused Ring Dichloro-Substituent Chalcone Isomers

The third-order nonlinear optical response of halogen anthracenyl chalcone isomersin dimethyl sulphonate (DMSO) as the solvent has been studied via single beam Zscan technique at 532 nm of laser excitation wavelength. The magnitude and sign of the nonlinear refractive index, n2 and the nonlinear absorption coefficient, β were determined. It was observed from the closed aperture z-scan that the samples exhibited a self-focusing effect with a negative n2. The n2 is found to be of the order of 10−8 cm2 /W. Open z-scan results showed that both samples exhibited reverse saturable absorptions with significant β. The magnitude of β is of the order of 10-4 cm/W. Optical limiting studies shows a decrement in transmittance as a function of input fluence. Optical limiting action begins at as low as 50 kW/cm2 of focal input intensity which is ideal for low powered continuous wave laser limiting applications. These attractive third-order nonlinear properties suggest that the compound can be a good candidate for optoelectronic and photonics application

Fused ring effect on optical nonlinearity and structure property relationship of anthracenyl chalcone based push-pull chromophores

The Ultraviolet-visible (UV-Vis) spectra indicate that anthracenyl chalcones (ACs) have high maximum wavelengths and good transparency windows for optical applications and are suitable for optoelectronic applications owing to their HOMO–LUMO energy gaps (2.93 and 2.76 eV). Different donor substituents on the AC affect their dipole moments and nonlinear optical (NLO) responses. The positive, negative, and neutral electrostatic potential regions of the molecules were identified using molecular electrostatic potential (MEP). The stability of the molecule on account of hyperconjugative interactions and accompanying charge delocalization was analyzed using natural bond orbital (NBO) analysis. Open and closed aperture Z-scans were performed using a continuous-wave frequency-doubled diode-pumped solid-state (DPSS) laser to measure the nonlinear absorption and nonlinear refractive index coefficients, respectively. The valley-to-peak profile of AC indicated a negative nonlinear refractive index coefficient. The obtained single crystals possess reverse saturation absorption due to excited-state absorption. The structural and nonlinear optical properties of the molecules have been discussed, along with the role of anthracene substitution for enhancing the nonlinear optical properties. The calculated third-order susceptibility value was 1.10 x10-4 esu at an intensity of 4.1 kW/cm2, higher than the reported values for related chalcone derivatives. The NLO response for both ACs offers excellent potential in optical switching and limiting applications

The effect of the fused-ring substituent on anthracene chalcones: crystal structural and DFT studies of 1-(anthracen-9-yl)-3-(naphthalen-2-yl)prop-2-en-1-one and 1-(anthracen-9-yl)-3-(pyren-1-yl)prop-2-en-1-one

The title chalcone compounds, C27H18O (I) and C33H20O (II), were synthesized using a Claisen–Schmidt condensation. Both compounds display an s-trans configuration of the enone moiety. The crystal structures feature intermolecular C—H...O and C—H...π interactions. Quantum chemical analysis of density functional theory (DFT) with a B3LYP/6–311++G(d,p) basis set has been employed to study the structural properties of the compound. The effect of the intermolecular interactions in the solid state are responsible for the differences between the experimental and theoretical optimized geometrical parameters. The small HOMO–LUMO energy gap in (I) (exp : 3.18 eV and DFT: 3.15 eV) and (II) (exp : 2.76 eV and DFT: 2.95 eV) indicates the suitability of these compounds for optoelectronic applications. The intermolecular contacts and weak contributions to the supramolecular stabilization are analysed using Hirshfeld surface analysis

Crystal structure and theoretical studies of two π-conjugated fused-ring chalcones: (E)-1-(anthracen-9-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one and (E)-1-(anthracen-9-yl)-3-[4-(9H-carbazol-9-yl)phenyl]prop-2-en-1-one

The title chalcones, C31H23NO and C35H23NO, were synthesized via Claisen–Schmidt condensation reactions. Both structures were solved and refined using single-crystal X-ray diffraction data and optimized at the ground state using the density functional theory (DFT) method with the B3LYP/6-311++G(d,p) level. In the crystals, π–π interations and weak C—H...O and C—H...π interactions are observed. The effect of these intermolecular interactions in the solid state can be seen by the difference between the experimental and theoretical optimized geometrical parameters. The structures have also been characterized by UV–Vis spectroscopy. The smallest energy gaps of 2.86 and 2.96 eV enhance the nonlinear responses of such molecular systems. Hirshfeld surface analyses and 2D (two-dimensional) fingerprint plots were used to quantify the intermolecular interactions present in the crystal, indicating that these are the most important contribution to the crystal packing

Molecular structure, DFT studies and Hirshfeld analysis of anthracenyl chalcone derivatives

The molecular and crystal structure of two new chalcone derivatives, (E)-1-(anthracen-9-yl)-3-[4-(piperidin-1-yl)phenyl]prop-2-en-1-one, C28H25NO, (I), and (E)-1-(anthracen-9-yl)-3-[4-(diphenylamino)phenyl]prop-2-en-1-one, C35H25NO, (II), with the fused-ring system at the same position are described. In the crystals of (I) and (II), the molecules are linked via C—H...O hydrogen bonds into inversion dimers, forming R22(22) and R22(14) ring motifs, respectively. Weak intermolecular C—H...π interactions further help to stabilize the crystal structure, forming a two-dimensional architecture. The molecular structures are optimized using density functional theory (DFT) at B3LYP/6–311 G++(d,p) level and compared with the experimental results. The smallest HOMO–LUMO energy gaps of (I) (exp . 2.76 eV and DFT 3.40 eV) and (II) (exp . 2.70 eV and DFT 3.28 eV) indicates the suitability of these crystals in optoelectronic applications. All intermolecular contacts and weaker contributions involved in the supramolecular stabilization are investigated using Hirshfeld surface analysis. The molecular electrostatic potential (MEP) further identifies the positive, negative and neutral electrostatic potential regions of the molecules

Crystal structure, spectroscopic characterization and DFT study of two new linear fused-ring chalcones

The structures of two new anthracenyl chalcones, namely (E)-1-(anthracen-9-yl)-3-(4-nitrophenyl)prop-2-en-1-one, C23H15NO3, and (E)-1-(anthracen-9-yl)-3-(4-iodophenyl)prop-2-en-1-one, C23H15IO are reported. A structural comparative study between the two chalcones was performed and some effects on the geometrical parameters, such as planarity and dihedral angles, are described. The molecular geometry was determined by single-crystal X-ray diffraction, and density functional theory (DFT) at B3LYP with the 6–311++G(d,p) basis set was applied to optimize the ground-state geometry. In addition, intermolecular interactions responsible for the crystal packing were analysed. The electronic properties, such as excitation energies and HOMO–LUMO energies were calculated by time-dependent density functional theory (TD–DFT) and the results complement the experimental findings. The molecular electrostatic potential (MEP) was also investigated at the same level of theory in order to identify and quantify the possible reactive sites

Crystal structures, DFT studies and UV–visible absorption spectra of two anthracenyl chalcone derivatives

The crystal structures of (E)-1-(anthracen-9-yl)-3-(3H-indol-2-yl)prop-2-en-1-one, C25H17NO, and (E)-1-(anthracen-9-yl)-3-[4-(dimethylamino)naphthalen-1-yl]prop-2-en-1-one, C29H23NO, are reported. In each case the anthracene ring system and pendant ring system are almost perpendicular to each other [dihedral angles = 75.57 (7)° and 70.26 (10)°, respectively]. In the extended structures, weak N—H...O, C—H...O and C—H...π interactions influence the centrosymmetric crystal packing. Density functional theory calculations were carried out using a 6–311 G++(d,p) basis set and the calculated structures are in good agreement with the crystal structures. The compounds were also characterized by UV–Vis absorption spectroscopy and the smallest (HOMO–LUMO) energy gaps of 2.89 and 2.54 eV indicate the enhanced non-linear responses (intermolecular charge transfers) of these systems

Experimental and theoretical spectroscopic and structural analyses of a new chalcone single crystal derived from 4-bromo-2-thiophenecarboxaldehyde

<p>A new chalcone compound, (<i>E</i>)-1-([1,1′-Biphenyl]-4-yl)-3-(4-bromothiophen-2-yl)prop-2-en-1-one (<b>BBTP</b>), crystallizes in the monoclinic space group <i>P</i>2₁/c and its structure has been characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and ultraviolet and visible (UV-Vis) absorption spectroscopy. The structural and spectroscopic analyses of the chalcone were calculated using DFT/B3LYP method. Molecular structure, crystal structure arrangement, and intermolecular hydrogen bond interactions were determined by single crystal X-ray diffraction method. In the crystal packing, intermolecular C‒H···O hydrogen bonds and C‒H···π interaction formed infinite two-dimensional sheets, thus strengthening the crystal structure. Hirshfeld surface analysis, HOMO-LUMO, and molecular electrostatic potential results are also reported.</p

Comparative analyses of new donor-π-acceptor ferrocenyl-chalcones containing fluoro and methoxy-fluoro acceptor units as synthesized dyes for organic solar cell material

Two organometallic compounds known as (E)-1-ferrocenyl-(3-fluorophenyl)prop-2-en-1one (Fc1) and (E)-1-ferrocenyl-(3-fluoro-4-methoxyphenyl)prop-2-en-1-one (Fc2) are designed and synthesized for application in dye-sensitized solar cell (DSSC) based on a donor-π-acceptor (D-π-A) architecture. By strategically introducing a methoxy group into the acceptor side of the compound, Fc2 which has adopted a D-π-A-AD structure are compared with the basic D-π-A structure of Fc1. Both compounds were characterized by utilizing the IR, NMR and UV-Vis methods. Target compounds were further investigated by X-ray analysis and studied computationally using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) approaches to explore their potential performances in DSSCs. An additional methoxy group has been proven in enhancing intramolecular charge transfer (ICT) by improving the planarity of Fc2 backbone. This good electronic communication leads to higher HOMO energy level, larger dipole moment and better short-circuit current density (Jsc) values. Eventually, the presence of methoxy group in Fc2 has improved the conversion efficiency as in comparison to Fc1 under the same conditions