•CPDAPP crystal is successfully grown by slow evaporation method.•CPDAPP crystal belongs to monoclinic crystal system with space group P21/c•The transparency, energy gap are determined by ...experimental and theoretical methods.•The thermal stability, FMOs, MEP and NBO of the chalcone are studied.•The optical limiting and third order NLO properties are determined in the CW regime•Dipole moment, polarizability and hyperpolarizability are calculated theoretically.•The optical behaviour of the crystal makes it suitable for fabrication of photonic devices.
A novel chalcone derivative (2E)-1-(4-chlorophenyl)-3-(4-diethylaminophenyl)-prop-2-en-1-one (CPDAPP) was synthesized and crystallized by slow evaporation growth method. Single crystal X-ray diffraction analysis confirmed the monoclinic system of the compound with P21/c space group. The molecular structure was confirmed by using FT-IR, FT-Raman, 1H NMR and 13C-NMR studies. Transparency of CPDAPP crystal was studied by UV-Vis spectrum analysis and band gap was found to be 2.7 eV. Thermo gravimetric analysis and DSC measurements revealed thermal stability, material decomposition and melting point of the grown crystal. Photoluminescence spectrum revealed emission peaks in green region. The third-order nonlinear optical properties of CPDAPP was investigated in DMF using Z-scan technique with continuous wave (CW) DPSS laser at 532 nm wavelength. The title chalcone exhibited significant two-photon absorption, negative nonlinear refraction (n2 = − 1.25 × 10−8 cm2W−1) and optical limiting threshold = 1.91 kW/cm2 under the CW regime. A comprehensive theoretical study was carried out on the molecule of CPDAPP using density functional theory (DFT) and compared with experimental results. The optimized geometry and frontier molecular orbitals were calculated by employing B3LYP/6-31++G(d,p) level of theory. The optimized molecular structure was confirmed computationally by IR and Raman vibrational and 1H NMR and 13C-NMR spectral analysis. The static NLO properties such as dipole moments (μ), polarizability (α), first (β) and second order hyperpolarizability (γ) were computed. The electronic excitation energies and HOMO–LUMO band gap for CPDAPP were also determined by DFT. The experimental and theoretical results were in good agreement and the NLO study shows that CPDAPP molecule can be a promising material for nonlinear optical applications.
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In this paper, we report enhancing the structural, morphological, mechanical, linear and nonlinear optical properties of polyvinyl alcohol (PVA) encapsulated with titanium dioxide (TiO2) and copper ...oxide (CuO) nanoparticles. PVA/(x)TiO2(15-x)CuO nanocomposites for x = 0 wt%, 1 wt%, 5 wt%, 7.5 wt%, 10 wt%, 14 wt% and 15 wt% filling concentration are prepared using ex-situ and solvent casting technique. The XRD spectra of the prepared nanocomposites endorse the semi-crystalline nature of PVA nanocomposites. The atomic force microscope (AFM) image displayed the uniform grain structure for pure PVA and change in surface morphology for prepared nanocomposites. Universal testing machine (UTM) explored high tensile strength and Young's modulus of 1685.70 MPa for x = 10 wt% filling concentration. PVA/(x)TiO2(15-x)CuO nanocomposites shows an enhanced electrical conductivity of 3.21 × 10−8Scm−1 for x = 10 wt% filling concentration. UV–Vis spectroscopy exposed the reduction in optical energy gap with the increase in filling concentration. Photoluminescence (PL) studies spectacles maximum enhancement in PL intensity for x = 10 wt% filling concentration. The Z-scan technique shows third order nonlinear absorption coefficient of 8.17 × 10−4 cm/W, the nonlinear refractive index of 2.56 × 10−8 cm2/W and nonlinear optical susceptibility of 1.48 × 10−6 esu for optimum nanocomposites.
•XRD spectra confirm the formation of semi crystalline nature of the nanocomposites.•PL studies shows an intense emission band at 680 nm resemble the electron hole recombination of TiO2 and CuO nanoparticles.•Dielectric studies exposes the maximum real dielectric constant value 7.5 for x = 10 wt% filling concentration.•NLO studies show material exhibit strong two-photon absorption and high third order Non-linear optical susceptibility.
In the present work, the title chalcone, (2E)-3-(4-fluorophenyl)-1-(4-{(1E)-(4-fluorophenyl) methyleneamino}phenyl)prop-2-en-1-one (abbreviated as FAMFC), was synthesized and structurally ...characterized by single-crystal X-ray diffraction. The compound is crystallized in the monoclinic system with non-centrosymmetric space group P21 and hence it satisfies the essential condition for materials to exhibit second-order nonlinear optical properties. The molecular structure was further confirmed by using FT-IR and 1H NMR spectroscopic techniques. The title crystal is transparent in the Vis-NIR region and has a direct band gap. The third-order nonlinear optical properties were investigated in solution (0.01M) by Z-scan technique using a continuous wave (CW) DPSS laser at the wavelength of 532nm. The title chalcone exhibited significant two-photon absorption (β=35.8×10−5cmW−1), negative nonlinear refraction (n2=−0.18×10−8cm2W−1) and optical limiting (OL threshold=2.73kJcm−2) under the CW regime. In support of the experimental results, a comprehensive theoretical study was carried out on the molecule of FAMFC using density functional theory (DFT). The optimized geometries and frontier molecular orbitals were calculated by employing B3LYP/6-31+G level of theory. The optimized molecular structure was confirmed computationally by IR vibrational and 1H NMR spectral analysis. The experimental UV–Vis-NIR spectrum was interpreted using computational chemistry under time-dependent DFT. The static and dynamic NLO properties such as dipole moments (μ), polarizability (α), and first hyperpolarizabilities (β) were computed by using finite field method. The obtained dynamic first hyperpolarizability β(−2ω;ω,ω) at input frequency ω=0.04282a.u. is predicted to be 161 times higher than urea standard. The electronic excitation energies and HOMO–LUMO band gap for FAMFC were also evaluated by DFT. The experimental and theoretical results are in good agreement, and the NLO study suggests that FAMFC molecule can be a potential candidate in the nonlinear optical applications.
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•FAMFC is crystallized in the monoclinic system with non-centrosymmetric space group P21.•The crystal is transparent in the Vis-NIR region and has a direct band gap.•The first order hyperpolarizability is predicted to be 161 times higher than urea standard.•FAMFC exhibits significant TPA, negative NLR and OL under the CW regime.
Experimental and computational studies of linear and nonlinear optical (NLO) properties of (2E)‐3‐(5‐bromo‐2‐thienyl)‐1‐(4‐nitrophenyl)prop‐2‐en‐1‐one (5B2SNC) single crystals are reported. ...Good‐quality and large‐sized single crystals of 5B2SNC were successfully grown and characterized by powder X‐ray diffraction and high‐resolution X‐ray diffractometry techniques. 5B2SNC was found to crystallize in the monoclinic noncentrosymmetric space group Cc and possesses moderately good crystalline perfection. The linear optical properties were investigated using the absorption spectrum, which reveals a direct optical band gap of 3.1 eV. The thermal stability was studied with thermogravimetric analysis/differential thermal analysis. The powder second harmonic generation efficiency was evaluated by the Kurtz and Perry method, and 5B2SNC was found to be 26 times more efficient than urea standard. Third‐order NLO properties were studied by the z‐scan technique with a femtosecond laser. The second hyperpolarizability was obtained to be ∼1.45 × 10−31 e.s.u. The molecule reveals a strong reverse saturation absorption and negative nonlinear refraction. The molecule exhibited good optical limiting properties, and its limiting threshold was measured to be ∼3.2 mJ cm−2. In addition, static electric dipole moments, linear polarizabilities, and first‐ and second‐order hyperpolarizabilities were calculated by density functional theory (DFT). Highest occupied molecular orbital/lowest unoccupied molecular orbital band gaps were also evaluated by DFT calculations. The experimental and theoretical results showed that 5B2SNC exhibits excellent second‐ and third‐order nonlinear optical properties.
In the current work, the experimental and quantum chemical approach has been applied to a 5‐bromo‐2‐thienyl‐4′‐nitrochalcone derivative which possesses good nonlinear optical properties.
Herein we report the crystal structure geometry, optoelectronic and charge transport properties of (E)-1-(4-Bromophenyl)-3-(2-chlorophenyl)prop-2-en-1-one (1), ...(E)-3-(3-Bromophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (2) and (E)-3-(4-Chlorophenyl)-1-(2-furyl)prop-2-en-1-one (3) chalcone derivatives. In experimental part UV–vis-NIR, X-ray diffraction and Photoluminescence spectroscopy techniques were used. Additionally, quantum chemical density functional theory calculations were executed with a clear view to explore the linear optical, second and third-order nonlinear optical (NLO) properties as well as transfer integrals of all three systems. The experimental and theoretically calculated properties are found to be in excellent accord with each other. Comprehensible intra- and inter-molecular charge transport was observed from occupied to unoccupied molecular orbitals illuminating that these chalcones would be good choice to be used in various semiconductor devices. The compound (3) is found to have better NLO activities and thermal stability compared to (1) and (2). Larger electron transfer integral values than hole ones exposed that studied compounds would be better electron transport materials and can function as n-type in organic semiconductor devices.
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•(002) oriented Zn1-xCoxO films were prepared using 0.0125 M solutions molarity.•Surface morphology changed from fibrous to rice like structure.•XPS analysis confirm the existence of ...Co2+ state.•Transmittance and energy band gap decreases with increase of dopant.•Reduction of optical limiter nature with increase in the Co doping.
The spray pyrolyzed Zn1−xCoxO (x = 0.01–0.10 at%) (ZCO) films showed polycrystalline nature with a prominent peak of (002) plane. Fibrous structure changes to the rice-grain type morphology with an increase in doping. XPS analysis confirmed the existence of Co ions in the +2 state. The transmittance and energy bandgap (Eg) of deposits reduces with an increase in doping level due to Co2+. The Z-scan technique was used to measure the third-order optical nonlinearities using DPSS CW laser at 532 nm excitation wavelength. The calculated third-order nonlinear susceptibility χ(3) is in the order of ~10−7 esu. The measured optical limiting threshold is in the range of 5.8–9.6 kJ/cm2. The deposits can be used in light sensitive devices for optical limiter application.
A novel organic crystal namely (2E, 4E)-dimethylamino) phenyl-1-(4methylphenyl) penta-2, 4-dien-1-one has been grown successfully from the slow evaporation method. The single-crystal X-ray ...diffraction study revealed that the compound belongs to the orthorhombic crystallographic system with non-centrosymmetric P
212121
space group with lattice parameters α = 7.1354(3) Å, β = 11.2112(7) Å and 20.0744(11) Å. The thermal properties have been studied by using Thermo Gravimetric (TG) and Differential Scanning calorimetry (DSC). The second harmonic generation (SHG) efficiency of the compound is 2.9 times that of urea for Nd-YAG laser operating at wavelength 1064 nm. We also report the results of thermally induced third-order nonlinear optical (NLO) properties of NLO material investigated by Z-scan technique using continuous wave (CW) laser. The calculated values of
χ
R
(
3
)
(
esu
)
,
χ
i
(
3
)
(
esu
)
and
χ
(
3
)
are of the order of 10
−7
esu, 10
−8
esu and 10
−7
esu, respectively. The estimated value of the non-linear refractive index is found to be − 4.21 × 10
−8
cm
2
/W. The compound also exhibits promising optical limiting properties at 532 nm wavelength.
Graphic abstract
The synthesis and structural characterization of a new D-π-A-π-D Nonlinear Optical material namely (2E, 4E)-dimethylamino) phenyl-1-(4methylphenyl)penta-2,4-dien-1-one Crystal is reported. The material can be utilized for both second and third-order nonlinear applications.
•The incorporation of thienyl ring in chalcone backbone enhances nonlinear absorption, nonlinear refraction, and optical limiting responses relative to phenyl ring.•A stronger push-pull effect is ...revealed through electrostatic potential analysis and the greater electron delocalization is demonstrated by π-electron localization function analysis (ELF-π).•A lower energy barrier for electronic transitions is indicated by the smaller HOMO-LUMO energy gap (EH-L) and optical energy gap (Eg).•The intramolecular charge transfer mechanism of charge-transfer (CT) type excitations is established via hole-electron distribution and interfragmentary charge transfer analyses.
This paper presents the effects of incorporating thienyl and phenyl rings as the terminal ring in the cinnamoyl counterparts of chalcones with donor-acceptor-donor (D-A-D) push-pull setting, on their photophysical responses. Two fluoro-methoxy substituted chalcone derivatives with distinct cinnamoyl systems, 4-methylthiophene-2-carbaldehyde (2F4MA48) and 2,4-dimethylbenzaldehyde (2F4MA96), were synthesized. Characterization of these chalcone derivatives was performed using nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) and single-crystal X-ray diffraction (SCXRD). Comparative studies on the linear and nonlinear optical responses were carried out through both experimental analyses and theoretical density functional theory (DFT) calculations. The electronic absorption spectra computed using DFT were compared with the UV-Vis spectra to elucidate the intramolecular charge transfer mechanism via the hole-electron distribution and interfragmentary charge transfer analyses. Molecular properties were examined through electrostatic potential (ESP) maps, π-electron localization function (ELF-π), and frontier molecular orbitals (FMOs). The incorporation of thienyl ring is found to give a stronger push-pull effect and greater electron delocalization. Experimental nonlinear optical responses were investigated using Z-scan technique with a continuous-wave incident laser at a wavelength of 532 nm. Both compounds showed two-photon-induced reverse saturation absorption (RSA) and self-defocusing responses. It was observed that the thienyl-based chalcone, exhibited greater optical nonlinearity in terms of nonlinear absorption (NLA), nonlinear refraction (NLR), and optical limiting. The experimental third-order nonlinear optical susceptibility (χ(3)) was determined to be 8.04 × 10−8 esu for 2F4MA48 and 1.08 × 10−8 esu for 2F4MA96. The onset limiting threshold (FS) was found to be 2.63 kJ cm−2 for 2F4MA48 and 5.23 kJ cm−2 for 2F4MA96. The steep optical limiting traces of 2F4MA48 show superior performance compared to 2F4MA96.
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In the present study, third-order nonlinear optical properties of three chalcone derivatives, (2E)-3-(4-methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one (MNC), ...(2E)-3-(4-methylphenyl)-1-(3-nitrophenyl)prop-2-en-1-one (ML3NC) and (2E)-3-(3,4-dimethoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (DMMC) doped Poly(methyl methacrylate) (PMMA) thin films are reported. The thin films were prepared using spin-coating technique at three different doping concentrations. Surface roughness and linear optical properties of the films were studied by atomic force microscopy (AFM) and UV-Vis-NIR absorption spectrum, respectively. The intermolecular interactions of the chalcones were studied using Hirshfeld surface analyses (HSA). The third-order nonlinear optical (NLO) properties of the films were investigated by using Z-scan technique with DPSS continuous wave (CW) laser excitation at 532 nm. All the films exhibited strong nonlinear absorption (NLA) behavior, and the obtained nonlinear absorption coefficients (β) increases with doping concentration of chalcones. Further, we observed the optical limiting property for all the films, which is mainly originated from two-photon absorption (TPA) mechanism. The calculated third-order nonlinear absorption coefficients (β), imaginary part of third-order nonlinear susceptibilities (Im χ(3)) and the optical limiting (OL) thresholds of the films are in the order of 10−5 cm/W, 10−8 esu and 103 J/cm2, respectively. The results revealed that the chalcones doped PMMA thin films are promising materials for optical limiting applications in visible region.
•Chalcones doped PMMA thin films were prepared by using spin-coating method.•The films are optically transparent in the wavelength region 450–900 nm.•The β and χ(3) values are in the order of 10−5 cmW−1 and 10−8 esu, respectively.•The NLO properties of the films increase with doping concentration of the chalcones.
We report the linear optical and third-order nonlinear optical (NLO) properties of three anthracene chalcone derivatives, (E)-1-(anthracene-9-yl)-3-(4-bromophenyl)prop-2-en-1-one (Br-ANC), ...(E)-1-(anthracene-9-yl)-3-(4-chlorophenyl)prop-2-en-1-one (Cl-ANC) and (E)-1-(anthracene-9-yl)-3-(4-nitrophenyl)prop-2-en-1-one (N-ANC) doped poly(methyl methacrylate) (PMMA) polymer thin films. The chalcones doped PMMA thin films were prepared using chemical spray pyrolysis technique at 10 wt%, 20 wt%, and 30 wt% doping concentrations. The linear absorption, transmittance, and refractive index of the films were measured using UV–vis-NIR spectra. The surface roughness of the films were studied by atomic force microscopy (AFM). The NLO properties of the films were investigated by Z-scan technique using continuous wave (CW) laser operating at 532 nm wavelength. A saturable absorption and self-defocusing effects were observed from the open and closed aperture Z-scan curves, respectively. The calculated nonlinear refractive index (n2∼10−9 cm2/W), nonlinear absorption coefficient (β∼10−3 cm/W) and third-order nonlinear optical susceptibility (χ(3) ∼10−7 esu) of the films increases with increase in the doping concentration of chalcones. Further, we observed relatively higher nonlinearity for N-ANC doped PMMA thin films than that of Br-ANC and Cl-ANC, which demonstrates an enhancement in optical nonlinearities by simple structural variations. The observed tunable saturable absorption behavior of chalcones doped PMMA thin films with larger magnitude and lower saturation intensity make them suitable candidates for mode-locking, Q-switching and laser cavity applications.
