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Facile synthesis of extended TPA-quinazolinone derivatives and the nonlinear optical properties
摘要： In this work, four new quinazolinone(QZ)-based compounds containing triphenylamine (TPA) moiety have been synthesized, defined as QZC, QZC-1, QZC-2, QZC-3, for the application of third-order nonlinear optical (NLO) responses. A new design of two-step synthesis has been put forward, the first step is Ullmann reaction with QZ, and the second is connecting QZ and the substituted triphenylamines (TPAs) through a Suzuki cross-coupling reaction to afford the target products. Electrochemical measurement data indicated that the tuning of the HOMO and LUMO energy levels can be easily achieved by introducing and modifying the donor moiety. The NLO properties were evaluated by the Z-scan technique which showed that introduction of a benzene ring as a π bridge could reduce the transmission energy of electrons from a ground state to an excited state, and the added methoxy in TPA moiety could promote the ICT, and improve the third-order NLO properties of molecules. Theoretical calculations matched well with the electrochemical information and NLO information. The results suggest that the materials based on QZ have potential applications in integrated NLO devices.
关键词： Fluorescence,photophysical property,Extended Quinazolinone derivative,third-order NLO material,Z-scan technology
更新于2025-11-19 16:46:39
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Twins in YAl3(BO3)4 and K2Al2B2O7 Crystals as Revealed by Changes in Optical Activity
摘要： Many borate crystals feature nonlinear optical properties that allow for efficient frequency conversion of common lasers down into the ultraviolet spectrum. Twinning may degrade crystal quality and affect nonlinear optical properties, in particular if crystals are composed of twin domains with opposing polarities. Here, we use measurements of optical activity to demonstrate the existence of inversion twins within single crystals of YAl3(BO3)4 (YAB) and K2Al2B2O7 (KABO). We determine the optical rotatory dispersion of YAB and KABO throughout the visible spectrum using a spectrophotometer with rotatable polarizers. Space-resolved measurements of the optical rotation can be related to the twin structure and give estimates on the extent of twinning. The reported dispersion relations for the rotatory power of YAB and KABO may be used to assess crystal quality and to select twin-free specimens.
关键词： optical activity,inversion twin,YAB,optical rotatory dispersion,KABO,second harmonic generation,frequency conversion,K2Al2B2O7,NLO crystals,YAl3(BO3)4
更新于2025-10-22 19:40:53
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2-(1,1-dioxidobenzo[b]thiophen-3(2H)-ylidene)malononitrile (BTD) Based Styryl Chromophores- Solvatochomic and Computational Investigation of Linear and NLO properties
摘要： Linear and nonlinear optical properties of the twelve styryl dyes are investigated using density functional theory (DFT). Range-separated hybrid CAM-B3LYP and global hybrid BHandHLYP estimate high second order hyperpolarizability. Mean polarizability (α0), polarizability anisotropy (Δα), static first-order hyperpolarizability (β0) and second hyperpolarizability (γ) were found to be overestimated in CAM-B3LYP than in BHandHLYP. As bond length alternation (BLA) increases first order hyperpolarizability increases. Multilinear regression analysis (MLR) shows the solvent basicity, polarizability and dipolarizability are responsible for absorption solvatochromism. The ratio of the dipole moments increases as donor strength and conjugation increases which support charge transfer. The figure of merit (FOM) and intrinsic hyperpolarizability found more in chromophores with dialkylamine donors. As the stability indicated by electrophilicity indices decreases the hyperpolarizability increases. Interrelationships between α0, β0 and γ were evaluated and it shows good linear fit. Absorption is red shifted and hyperpolarizability increases with the amplitude of the sine-shaped potential along the conjugation chain. A high molecular electrostatic potential was observed in dyes containing 2-piperidinothiophene donor.
关键词： NLO,Charge transfer,DFT and TD-DFT,Absorption,Solvatochromism
更新于2025-09-23 15:23:52
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Structure, Reactivity, Nonlinear Optical Properties and Vibrational Study of 5-Thioxo-1,4-thiazaolidin-3-one and 5-thioxo-1,4,2-thiazasilolidin-3-one (Silicon vs. Carbon). A DFT Study
摘要： The structures and nonlinear optical properties (NLO) of 5-thioxo-1,4-thiazaolidin-3-one(Rhodanine) and 5-thioxo-1,4,2-thiazasilolidin-3-one (silarhodanine) tautomers were studied in gas phase and in solutions using the B3LYP density functional theory and composite CBS-QB3 method. The global minimum at the B3LYP/6-31++G(d,p) and CBS-QB3 levels of theory is tautomer 5 in the gas phase and in solvents for rhodanine, and simiarly, tautomer 13 is the global minimum for silarhodanine. The interconversion among the tautomers is proceeded by an intramolecular proton transfer reaction. An identical solvent effects can be noted for rhodanine and silarhodanine tautomers. The activation barrier towards ring-opening processes (1→2, 9→10) decreases with the increasing dielectric constant of the solvent; on the other hand, the barrier of the ring-closure processes (2→3, 10→11) increases with the increasing dielectric constant. The tautomers are predicted to show significant NLO properties. Also, a number of correlations between the dipole moment and electron densities in bond critical points of the S3-C4 bond and interaction energy as well as vibrational frequencies at the transition states (TS2–3,TS10–11) were examined under different solvents. Finally, the investigation of the heavy atom substitution effects on the properties of silarhodanine is proven to be very weak under these conditions.
关键词： Vibrational assignments,Silarhodanine,Reactivity,Rhodanine,NLO,Ring-opening,Solvent effects
更新于2025-09-23 15:23:52
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Prediction of Structural, Vibrational and Nonlinear Optical Properties of Small Organic Conjugated Molecules Derived From Pyridine
摘要： Nonlinear optical (NLO) effects of organic materials are caused by delocalized electrons and large polarization in molecules. In the present work, theoretical study by using the Density Functional Theory (DFT) at B3LYP/6-311G(d,p) level of theory on three types of pyridine derivates 2,6-dimethoxy-3,5-dinitropyridine (M1), 2-methoxy-3-nitropyridine (M2) and 2-methoxy-5-nitropyridine (M3) is reported. The nuclear magnetic resonance (1H- and 13C-NMR) chemical shifts of the title compounds were calculated using the Gauge Independent Atomic Orbital (GIAO) method and compared to the observed results. Both infrared absorption and Raman are complementary to provide characteristic fundamental vibrations that are necessary for the identification of the molecular structures. Electronic properties such as frontier molecular orbital (HOMO, LUMO), ionization potential (IPad) and electronic affinity (EAad) were determined to get better insight into the molecular properties. Using the Time-Dependent Density Functional Theory (TD-DFT), electronic absorption spectra have been predicted and closely matching the experimental findings. The natural bonding orbital (NBO) calculations were performed in order to elucidate various second order interactions in between the filled and vacant orbitals which are a measure of the intermolecular as well as the delocalization within the molecule. In addition, we have demonstrated that these molecular systems have large first static hyperpolarizabilities and may have potential applications in the development of NLO materials.
关键词： NLO properties,Electronic properties,DFT,Optical spectra,NBO
更新于2025-09-23 15:23:52
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A Facile Route for NLO Materials: Three-Site Alivolent Substitution Involving One Cation and Two Anions
摘要： Two mixed-metal gallium iodate fluorides, namely, α- and β-Ba2[GaF4(IO3)2](IO3) (1 and 2) have been obtained by the aliovalent substitutions of α- and β-Ba2[VO2F2(IO3)2](IO3) (3 and 4) involving one cationic and two anionic sites. Both of them display large SHG signals (~6 × KDP), large energy bandgaps (4.61 and 4.35 eV), wide transmittance ranges (~0.27-12.5 μm), and large relevant LDTs (29.7 × and 28.3 × AgGaS2, respectively), which indicates that 1 and 2 are potential second-order NLO materials in ultraviolet to mid-infrared. Our studies propose that three-site aliovalent substitution is a facile route for the discovery of good NLO materials.
关键词： aliovalent substitution,hydrothermal synthesis,NLO material,mixed-metal iodate fluoride,theoretical calculations
更新于2025-09-23 15:23:52
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Spectroscopic behavior, FMO, NLO and NBO analysis of two novel aryl boronic acid derivatives: Experimental and theoretical insights
摘要： Here we report, experimental and theoretical determination of ground and excited state dipole moments of aryl boronic acid derivatives, 2-Bromophenyl boronic acid (2BPBA) and 2-Isopropylphenyl boronic acid (2IPBA). In both the compounds, Bathochromicshift is observed with increasing solvent polarity indicating π →π* transition due to intermolecular charge transfer interactions. For both the compounds, the ground and excited sate dipole moments are parallel to each other. The excited state dipole moment (μe) is greater than ground state dipole moment (μg) for the compound 2IPBA where as for 2BPBA, excited state dipole moment (μe) is less than ground state dipole moment (μg). Further, experimentally obtained Δμ are compared with those using microscopic empirical solvent polarity (??????). In parallel, the use of Kamlet-Taft parameters to the solvent effect on spectral properties of 2BPBA and 2IPBA are also discussed. The molecular structure, Frontier Molecular Orbitals (FMO), Natural Bond Orbital (NBO) analysis, Non-Linear Optical (NLO) properties of 2BPBA and 2IPBA have been investigated using the (DFT) calculations with B3LYP/6?311++G (d, p) basis set. The chemical reactivity and kinetic stability of the compounds is shown by differences between the energy levels by analyses of Frontier molecular orbitals. The polarizability and hyperpolarizability computations determine the NLO properties, whereas Natural bond orbital (NBO) analysis showed proton transfer within the selected donor-acceptor depicting large energy of stabilization for the compounds under study.
关键词： Kamlet-Taft,FMO,MEP,ground and excited state dipole moments,Solvatochromic shift method,NBO and NLO
更新于2025-09-23 15:23:52
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Synthesis of 3,4-Biaryl-2,5-Dichlorothiophene through Suzuki Cross-Coupling and Theoretical Exploration of Their Potential Applications as Nonlinear Optical Materials
摘要： We report herein the efficient one-pot synthesis of 3,4-biaryl-2,5-dichlorothiophene derivatives (2a–2i) via a palladium-catalyzed Suzuki cross-coupling reaction. A series of thiophene derivatives were synthesized, starting from 3,4-dibromo-2,5-dichlorothiophene (1) and various arylboronic acids using Pd(PPh3)4 and K3PO4 with moderate to good yields. For further insights about the structure and property relationship, density functional theory (DFT) calculations were performed. A relaxed potential energy surface (PES) scan was performed to locate the minimum energy structure. A frontier molecular orbitals analysis was performed to explain the reactivity of all synthesized derivatives. As the synthesized derivatives had extended conjugations, therefore the first hyperpolarizability (βo) was calculated to investigate their potential as non-linear optical (NLO) materials and significant βo values were found for the 2b and 2g derivatives.
关键词： NLO,Pd (PPh3)4,thiophene,PES,density functional theory,Suzuki cross-coupling reaction
更新于2025-09-23 15:22:29
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Synthesis and Optical Properties of Dipolar Thiazole Derivatives Incorporating Nitro and Amino Substituents
摘要： We report the synthesis of two dipolar thiazole derivatives functionalized with nitro group as electron acceptor and amino group as electron donor, in order to study their optical properties in the UV-vis range. Their structures were verified by 1H NMR, 13C NMR, HRMS and FT-IR. The resulted thiazole derivatives have good thermal stability with decomposition temperature, Td of 320.20 °C and 284 °C for compounds 1 and 2 respectively. The absorbance bands of compound 2 in the UV-vis range are more red-shifted than that of compound 1 which made compound 2 could have high potential as a great organic NLO material.
关键词： NLO,Push-pull,Thiazole derivative,Thermal stability,Dipolar thiazole
更新于2025-09-23 15:22:29
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Exploring the spectral features and quantum chemical computations of a novel biologically active heterocyclic class of compound 2MEFPBA dye: Experimental and theoretical approach
摘要： Here we report, experimental and theoretical determination of ground and excited state dipole moments of the class of heterocyclic compound namely 2-Methoxy-5-fluoro phenyl boronic acid (2MEFPBA) dye. Bathochromic shift with increasing solvent polarity is observed indicating π →π* transition due to intermolecular charge transfer interactions. The ground and excited state dipole moments are found to be parallel to each other. The molecular structure, Frontier molecular orbital (FMO), Natural bond orbital (NBO) analysis and Nonlinear optical (NLO) properties of 2MEFPBA have been investigated using the Density Functional Theory with B3LYP/6?31 ++ g(d, p) basis set. Chemical reactivity and kinetic stability of 2MEFPBA are analyzed using F M O energy. Polarizability and hyperpolarizability computations are used to determine the NLO properties, whereas Natural bond orbital (NBO) analysis showed the proton transfer within the selected donor-acceptor depicting large energy of stabilization for the compound under study.
关键词： MEP,NBO,FMO,Solvatochromic ground and excited state dipole moments,and NLO.
更新于2025-09-23 15:22:29