Remarkable Nonlinear Properties of a Novel Quinolidone Derivative: Joint Synthesis and Molecular Modeling.

A novel 4(1H) quinolinone derivative (QBCP) was synthesized and characterized with single crystal X-ray diffraction. Hirshfeld surfaces (HS) analyses were employed as a complementary tool to evaluate the crystal intermolecular interactions. The molecular global reactivity parameters of QBCP were studied using HOMO and LUMO energies. In addition, the molecular electrostatic potential (MEP) and the UV-Vis absorption and emission spectra were obtained and analyzed. The supermolecule (SM) approach was employed to build a bulk with 474,552 atoms to simulate the crystalline environment polarization effect on the asymmetric unit of the compound. The nonlinear optical properties were investigated using the density functional method (DFT/CAM-B3LYP) with the Pople's 6-311++G(d,p) basis set. The quantum DFT results of the linear polarizability, the average second-order hyperpolarizability and the third-order nonlinear susceptibility values were computed and analyzed. The results showed that the organic compound (QBCP) has great potential for application as a third-order nonlinear optical material.

A new isostructural halogenated chalcone with optical properties.

Chalcones are organic compounds that present a number of properties. This study presents a comprehensive structural description of a new derivative of a chlorine-substituted chalcone in comparison with a bromine chalcone. Also, supermolecule and sum-over-state approach were used to describe the optical properties of these structures regarding the substitution of the bromine by the chlorine atom. In addition, the electrical properties, dipole moment, linear polarizability, and second IDRI hyperpolarizability were calculated. The linear refractive index and the third-order nonlinear macroscopic susceptibility were evaluated as a function of the applied electric field frequency. Furthermore, the quantum mechanics calculations that were implemented at the M06-2X/6-311++G(d,p) level of the theory for these isostructural chalcones indicate that the change in halogen atoms does not cause meaningful changes in their conformation. Finally, we can postulate that side-to-side and the antiparallel interactions are the interaction forces that drive the crystal growth for new isostructural chalcones. The NLO properties showed title compounds that are good candidates for use as NLO materials.

Theoretical study of solvent effects on the hyperpolarizabilities of two chalcone derivatives / Estudio teórico de los efectos de solvente sobre la hiperpolarizabilidad de dos derivados de la chalcona / Estudo teórico dos efeitos do solvente nas hiperpolarizabilidades de dois derivados da chalcona

Abstract The use of organic as nonlinear optical materials has been intensively explored in the recent years due to the ease of manipulation of the molecular structure and the synthetic flexibility regarding the change of substituent groups. In the present work, the linear and nonlinear properties of two chalcones derivatives (E)-1-(4-methylphenyl)-3-phenylprop-2-en-1-one (4MP3P) and (E)-1-(4-Nitrophenyl)-3-phenylprop-2-en-1-one (4NP3P), that differ by the substituent position at the phenyl ring, were studied in the presence of protic and aprotic solvents simulated by the Polarizable Continuum Model (PCM) at DFT/B3LYP/6-311+G(d) level. The static and dynamic (1064 nm) molecular parameters as the dipole moment, linear polarizability, first and second hyperpolarizabilities were studied as function of the solvent dielectric constant value. The geometrical behavior as the chemical bond angles, torsion angles, and partial charges distribution of the compounds were studied, including calculations of gap energies in various solvents. The obtained results revealed that the substituent change of CH3 (4MP3P) to NO2 (4NP3P) benefits the nonlinear optical properties of the compounds in the presence of the solvent media, the absolute values of the parallel first hyperpolarizability were the ones that present the greater variation.

Resumen El uso de materiales orgánicos como materiales ópticos no lineales se ha explorado intensamente en los últimos años, debido a la facilidad de manipulación de estas estructuras moleculares y la flexibilidad de síntesis en relación con el cambio de grupos sustituyentes. En el presente trabajo, las propiedades lineales y no lineales de dos derivados de chalcona (E)-1-(4-metilfenil)-3-fenilprop-2-en-1-ona (4MP3P) y (E)-1-(4-nitrofenil)-3-fenilprop-2-en-1-ona (4NP3P), los cuales difieren en la posición del sustituyente en el anillo de fenilo, se estudiaron en presencia de disolventes próticos y apróticos simulados por el Modelo Continuo Polarizable a nivel DFT/B3LYP/6-311+G(d). Además, se estudiaron parámetros moleculares estáticos y dinámicos (1064 nm) como el momento dipolar, la polarización lineal y la primera y la segunda hiperpolarización en función del valor constante dieléctrico del disolvente. El comportamiento geométrico se estudió como ángulos de enlace químico, ángulos de torsión y distribución de carga parcial de compuestos, incluidos los cálculos de energía de huecos en varios solventes. Los resultados mostraron que el cambio del sustituyente CH3 (4MP3P) a NO2 (4NP3P) beneficia las propiedades ópticas no lineales de los compuestos en presencia del medio solvente, los valores absolutos de la primera hiperpolarizabilidad paralela fueron los que presentaron la mayor variación.

Resumo O uso de materiais orgânicos como materiais ópticos não lineares tem sido intensamente explorado nos últimos anos, devido à facilidade de manipulação dessas estruturas moleculares e à flexibilidade de síntese em relação à mudança de grupos substituintes. No presente trabalho, as propriedades lineares e não lineares de dois derivados de chalconas (E)-1-(4-metilfenil)-3-fenilprop-2-en-1-ona (4MP3P) e (E)-1-(4-nitrofenil)-3-fenilprop-2-en-1-ona (4NP3P), que diferem pela posição do substituinte no anel fenil, foram estudados na presença de solventes próticos e apróticos simulados pelo Modelo Continuo Polarizável (PCM) no nível DFT/B3LYP/6-311+G(d). Os parâmetros moleculares estáticos e dinâmicos (1064 nm) como momento dipolar, polarizabilidade linear, primeira e segunda hiperpolarizabilidades foram estudados em função do valor da constante dielétrica do solvente. Estudou-se o comportamento geométrico como ângulos de ligação química, ângulos de torção e distribuição parcial de cargas dos compostos, incluindo cálculos de energias de gap em vários solventes. Os resultados obtidos revelaram que a mudança do substituinte de CH3 (4MP3P) para NO2 (4NP3P) beneficia as propriedades ópticas não lineares dos compostos na presença do meio solvente, os valores absolutos da primeira hiperpolarizabilidade paralela foram os que apresentaram a maior variação.

Hyperpolarizability studies and Hirshfeld surface analysis of two heterocyclic chalcones.

In this work, the nonlinear optical (NLO) properties of two heterocyclic chalcones, (E)-1-(5-chlorothiophen-2-yl)-3-(thiophen-2yl)-2-propen-1-one (CLTT) and (E)-1-(5-methylfuran-2-yl)-3-(5-methylthiophen-2-yl)prop-2en-1-one (2MFT), are investigated. Using an iterative electrostatic embedding approach via the Møller-Plesset perturbation (MP2) theory, the chalcone crystals were simulated and the polarization effects on the isolated molecules are investigated. The electrical parameters of CLTT and 2MFT as dipole moment and linear polarizability were calculated via MP2/6-311++G(d) and the second hyperpolarizability was obtained via DFT/CAM-B3-LYP/6-311++G(d) level. A significant influence of the molecular packing on the chalcone electric parameters was observed. The static linear refractive index and the third-order electric susceptibility of the compounds were calculated and compared with experimental results available for other chalcone derivatives, indicating the CLTT crystal as a promising candidate for NLO applications in photonic and optoelectronic devices. The Hirshfeld surface analysis has been used to quantify the intermolecular interactions of the molecular crystals. Additionally, the solvent medium effects on the electrical properties of the heterocyclic chalcones were also studied.

Using the Supermolecule Approach To Predict the Nonlinear Optics Potential of a Novel Asymmetric Azine.

Organic molecules with electron acceptors or withdrawal substituents terminal at π-conjugated system are promising candidates to be explored as materials with high linear and nonlinear optical properties. On the basis of these features, a novel asymmetric azine ( 7E, 8E)-2-(3-methoxy-4-hydroxy-benzylidene)-1-(4-nitrobenzylidene)hydrazineC15H13N3O4 (NMZ) was synthesized. The molecular structure of NMZ was elucidated by X-ray crystallography and the supramolecular arrangement was analyzed from Hirshfeld surface methodology. An iterative electrostatic scheme using a super molecule approach, where neighboring molecules are represented by charge points, was employed to investigate optical dipole moment (µ), the linear polarization (α) and the first (ß) and second (γ) hyperpolarizabilities. The NMZ crystallized in the centrosymetric space group P21/n and packs via combined O-H···O, C-H···O, and N···π interactions. The macroscopic property of third order χ(3) found for the NMZ is 298.62 times greater than values reported for chalcone derivative (2 E)-1-(3-bromophenyl)-3-[4 (methylsulfanyl)phenyl]prop-2-en-1-one. The results for NMZ indicate a good nonlinear optical effect.

Third-Order Nonlinear Optical Properties of a Carboxylic Acid Derivative.

We report a study of the structural and electrical properties of a carboxylic acid derivative (CAD) with structural formula C5H8O2 ((E)-pent-2-enoic acid). Using the M∆ller-Plesset Perturbation Theory (MP2) and the Density Functional Theory (DFT/CAM-B3LYP) with the 6-311++G(d,p) basis set the dipole moment, the linear polarizability and the first and second hyperpolarizabilities are calculated in presence of static and dynamic electric field. Through the supermolecule approach the crystalline phase of the carboxylic acid derivative is simulated and the environment polarization effects on the electrical parameters are studied. Static and dynamic estimation of the linear refractive index and the third-order nonlinear susceptibility of the crystal are obtained and compared with available experimental results. The characteristic vibrational modes and functional groups present in CAD were analyzed by Fourier Transform Infrared Spectrum (FTIR) in the region of 400-4000 cm-1. Through the Hirshfeld surface analysis the molecular structure and the vibrational modes properties of the CAD crystal are explored. The effects of solvent medium on the molecular properties are taken into account through the Polarizable Continuum Model (PCM). Also, the frontiers molecular orbitals, the band gap energy, and the global chemical reactivity descriptors are discussed. All the properties studied suggest that the present material may be considered for nonlinear optical material.

Solid state characterization and theoretical study of non-linear optical properties of a Fluoro-N-Acylhydrazide derivative.

In this work we determine the linear and non-linear optical properties of a Fluoro-N-Acylhydrazide derivative (FBHZ), using a combined supermolecule approach and an iterative scheme of electrostatic polarization, where the atoms of neighbouring molecules are represented by point charges. Our results for non-linear optics (NLO) are comparable to those found experimentally, suggesting that FBHZ constitutes an attractive object for future studies and for use as an interesting material for third-order NLO applications. The dynamic electrical properties of FBHZ in different solvent media are reported. Its molecular properties are closely related to supramolecular features; accordingly, we analysed all its crystal structure properties via intermolecular interactions in the solid state, using X-ray crystallography data and Hirshfeld surface (HS), including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and hot-stage microscopy (HSM), where the results reveal crystal stability in respect to temperature variation.

Effect of the crystalline environment on the third-order nonlinear optical properties of L-arginine phosphate monohydrate: a theoretical study.

A supermolecular approach combined with an iterative electrostatic scheme was employed to investigate the nonlinear optical properties of the hybrid L-arginine phosphate monohydrate crystal, the procedure being aided by DFT calculations. The supermolecular scheme basically treated the molecules surrounding the unit cell as point charges; this approximation results in rapid convergence, making it a feasible method. DFT functionals of different flavors were considered: B3LYP, B2PLYP, CAM-B3LYP, ωB97, and M06HF, utilizing the 6-311 + G(d) basis set. All functionals gave sufficiently accurate values for the dipole moment (µ) with respect to the experimental value 32(2) D. For the average linear polarizability ([Formula: see text]) and the total first hyperpolarizability (ß tot), good agreement was observed between the DFT-calculated values and MP2-derived results reported in the literature. For the second hyperpolarizability, both static and dynamic regimes were considered. The point-charge embedding approach led to an attenuation of the second hyperpolarizability γ for all frequencies considered. Excitations of γ were not observed for frequencies smaller than 0.1 a.u. For the second hyperpolarizability (both static and dynamic), computational results showed that L-arginine phosphate monohydrate exhibits a large nonlinear optical effect, which implies the occurrence of microscopic third-order NLO behavior.