Organic Nonlinear Optical Material Research Articles

Group Contribution Method Supervised Neural Network for Precise Design of Organic Nonlinear Optical Materials

Group Contribution Method Supervised Neural Network for Precise Design of Organic Nonlinear Optical Materials

Third-order nonlinear optics and optical limiting of phenanthrenone derivatives

Organic nonlinear optical materials have attracted much attention due to their large nonlinear optical coefficients and ultrafast response speeds, as well as their potential applications in optical limiting (OL). Among them, nonlinear optical materials with phenanthrenone as the backbone are consistently understudied. We have successfully realized the transformation of organic small molecules in the nonlinear optical direction by replacing the carbonyl group on the structure of phenanthrenone with a malononitrile group. The nonlinear optical properties of CN-2 were investigated under different excitation conditions at 532 nm and the kinetic process of nonlinear optics was analyzed by transient absorption spectroscopy. In addition, we also investigated the OL properties of CN-2, and the OL experiments showed that CN-2 with a lower OL threshold has superior OL properties than C60.

Synthesis, Crystal Structure and Characterization of Organic Nonlinear Optical Material Benzophenone for Spectroscopic and Optoelectronics Applications

A novel crystal benzophenone’s nonlinear optical applications are pivotal. Benzophenone is one of the promising organic nonlinear optics materials for their high energy laser photonic application. It has already been possible to generate crystals of benzophenone in various ways. In this research, the slow evaporation method at room temperature was successful in making a single crystal of benzophenone. In this paper, synthesis, growth, characterization and applications of low melting organic nonlinear optics benzophenone crystal in order to improve their structural and physical properties are reported. Different characterization methods were applied to the grown crystals. The lattice parameters of the grown material were obtained by single crystal X-ray diffraction (XRD) study. The results of the single crystal XRD analysis showed that the produced crystals are a component of an orthorhombic system with the space group P212121 and the lattice parameters are [Formula: see text] Å, [Formula: see text] Å, [Formula: see text] Å, [Formula: see text] and [Formula: see text] Å3. Ultraviolet-visible (UV–Vis) spectrum indicates that the crystal is transparent (72%) in the entire visible region with a cutoff wavelength of 258[Formula: see text]nm. The transparency of the grown crystals has been confirmed using the UV–Vis spectrum. The second harmonic generation (SHG) efficiency of the grown crystal was measured using an Nd-YAG laser and it was found to be 1.8 greater than potassium dihydrogen orthophosphate (KDP). The FT-IR spectrum was examined in order to identify the many functional groups. The formation of the material was confirmed qualitatively by FT Raman spectral analyses. Mechanical properties such as Vicker’s microhardness number, Yield strength, Fracture toughness, Brittleness index and Elastic stiffness constant values were determined using Vicker’s microhardness test. The thermal stability of the grown crystal was studied by thermal analysis.

Crystal Growth and Characterisation of Strontium on Thiourea

Thiourea, being a potential organic Non-linear optical material with high SHG efficiency having application in laser technology and photonic applications are grown as single crystals of Strontium chloride doped thioureaby slow evaporation solution growth technique (SEST), one of the best method for crystal growth at room temperature. It is furtheranalysed by single crystal XRD which infers thatthe Strontium Chloride doped thiourea crystal has monoclinicsystem. The surface morphology was studied by SEM-EDS, that confirms thepresence of Strontium in the doped specimen. FTIR reveals some slight variation in vibrational frequencies and no secondaryvibrational bandsarefoundin the doped specimen indicating the presence of some dopant

Enhanced Characterisation Studies and Synthesis of Undoped and Copper Doped-Organic Nonlinear Optical Single Crystal: L-Alanine Aluminium Nitrate

Single crystals of untreated and copper (Cu2+) metal ion-doped L-alanine aluminium nitrate (LAAN), a room-temperature slow evaporation organic nonlinear optical material. Single crystals were studied for structural, spectral, optical, hardness, secondorder non-linear optical, electrical [(alternating current (AC) and direct current (DC)], and photoconductivity properties as they grew. Crystallinity, monoclinic structure with space collection P21, and lattice specifications were deliberate using single crystal X-ray diffraction investigation. The existence of functional clusters is revealed by the spectral properties, and the means of vibration of various molecular clusters existing in LAAN were evaluated using Fourier transform infrared (FTIR). The low cut-off wavelength and transmittance properties were determined using optical analysis. The band gap energy of LAAN and Cu-doped LAAN crystals was estimated to be 3.40 eV and 2.70 eV, respectively, using the Tauc plot. It was revealed that pure crystals had a lower dielectric constant than crystals that had been doped with copper. After doping with rising temperatures, AC conductivity started to rise. With the use of the Kurtz and Perry approach, the effectiveness of the grown crystal’s second harmonic generation was computed, Cu-doped LAAN was discovered to be 3.3 times more prominent than potassium dihydrogen phosphate (KDP) and 2.2 times more prominent than pure LAAN crystals. The nonlinear optical characteristics of LAAN crystals have therefore been improved by copper doping. It is most suited for use in electro-optic applications like laser technology, telecommunications and optical signal processing because of its negative photoconductivity.

Synthesis, crystal structures, spectroscopy, and quantum chemical studies on the 4-dimethylaminopyridinium-2,4-dinitrophenolate: an organic NLO material for optoelectronics.

In this work, the 4-dimethylaminopyridinium-2,4-dinitrophenolate (4DMAP + 2,4DNP) by slow evaporation solution growth method has been presented. The Fourier transform infrared (FT-IR) (4000-400cm-1) and FT-Raman (4000-50cm-1) spectra were recorded for the grown crystal. The computational calculation has been carried out with density functional theory (DFT) in ground state with Gaussian program package. Optimized geometrical parameters (bond distances, bond angles, and dihedral angles) have been obtained and compared with X-ray crystallography data. The calculated fundamental vibrational frequencies from DFT/B3LYP with 6-311 + + G(d,p) level of theory were scaled so as to agree with the observed results, and the scaling factors were reported. Experimental and computed ultraviolet-visible (UV-Vis) spectra in acetone and methanol solvents were found comparable to each other. Furthermore, the frontier molecular orbitals (FMOs) energies, molecular electrostatic potential (MEP), nonlinear optical (NLO), hirshfeld surface (HS), and global chemical descriptors of the molecule were also calculated. The thermal stability and the melting point of the title compound were analyzed by the thermogravimetric analysis/differential thermal analysis (TGA/DTA) techniques. The mechanical behavior of the organic single crystal was measured by Vickers micro-hardness method. The third-order nonlinear optical properties such as nonlinear refractive index (n2), nonlinear absorption coefficient (β), optical nonlinear susceptibility Reχ(3), and optical nonlinear susceptibility Imχ(3) were calculated by using the open and closed aperture Z-scan technique. The theoretical and experimental NLO values clearly proposed that the nonlinearity of 4DMAP + 2,4DNP molecule could be helped as a potential candidate for optical limiting, frequency doubling, and optical switching applications.

A Review on Synthesis, Lanthanide Complexes and Biological Activites of Hydrazone Derivatives of Hydrazinecarbothioamides

Hydrazinecarbothioamides are important intermediates with biological activities in organic chemistry synthesis, especially in the synthesis of biologically active heterocyclic scaffolds and compounds. The uniqueness in of synthesis and a wild range of pharmaceutical, medicinal biological potentials and properties, their preferred application as building brick in and the synthesis of heterocyclic and other important organic compounds and nonlinear optical (NLO) materials have made them attractive derivatives of thiosemicarbazides in the recent years. In this review, a detailed account in terms of synthesis and applications of their hydrazone derivatives and their lanthanide complexes are presented .Further, the biological and analytical applications of newly reported ligands and their complexes are reported. The wide investigation of the lanthanide (III) coordination complexes with organic ligands are mainly due to their structures and strong potential biological and pharmacological properties of hydrazones as derivatives of hydrazinecarbothioamides possess sites that play important roles in the formation of heterocyclics and other biologically active scaffolds.

Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

Optimization strategies for comprehensive performance of organic second-order nonlinear optical materials

Optimization strategies for comprehensive performance of organic second-order nonlinear optical materials

Durable organic nonlinear optical membranes for thermotolerant lightings and in vivo bioimaging

Organic nonlinear optical materials have potential in applications such as lightings and bioimaging, but tend to have low photoluminescent quantum yields and are prone to lose the nonlinear optical activity. Herein, we demonstrate to weave large-area, flexible organic nonlinear optical membranes composed of 4-N,N-dimethylamino-4ʹ-Nʹ-methyl-stilbazolium tosylate@cyclodextrin host-guest supramolecular complex. These membranes exhibited a record high photoluminescence quantum yield of 73.5%, and could continuously emit orange luminescence even being heated at 300 °C, thus enabling the fabrication of thermotolerant light-emitting diodes. The nonlinear optical property of these membranes can be well-preserved even in polar environment. The supramolecular assemblies with multiphoton absorption characteristics were used for in vivo real-time imaging of Escherichia coli at 1000 nm excitation. These findings demonstrate to achieve scalable fabrication of organic nonlinear optical materials with high photoluminescence quantum yields, and good stability against thermal stress and polar environment for high-performance, durable optoelectronic devices and humanized multiphoton bio-probes.

Design of the Ionic Organic Nonlinear Optical Material NH4 [LiC3 H(CH3 )O4 ] with Ultrawide Band Gap and Moderate Birefringence.

Ionic organic crystals containing organic planar π-conjugated units has become one of the hot spots as nonlinear optical (NLO) materials. However, although this type of ionic organic NLO crystals commonly have remarkable second harmonic generation (SHG) responses, they also suffer from overlarge birefringences and relatively small band gaps that be hardly beyond 6.2 eV. Herein, a flexible π-conjugated [C3 H(CH3 )O4 ]2- unit was theoretically revealed, showing great potential for designing NLO crystals with balanced optical properties. Accordingly, through the reasonable NLO-favourable layered design, a new ionic organic material, NH4 [LiC3 H(CH3 )O4 ], was successfully obtained. As expected, it achieves not only a large SHG effect (4×KDP), but also a suitable birefringence (0.06@546 nm) and an ultrawide band gap (>6.5 eV). This study provides a new flexible π-conjugated NLO-active unit, contributing to design more ionic organic NLO materials with excellent balanced optical properties.

Design of the Ionic Organic Nonlinear Optical Material NH4[LiC3H(CH3)O4] with Ultrawide Band Gap and Moderate Birefringence

AbstractIonic organic crystals containing organic planar π‐conjugated units has become one of the hot spots as nonlinear optical (NLO) materials. However, although this type of ionic organic NLO crystals commonly have remarkable second harmonic generation (SHG) responses, they also suffer from overlarge birefringences and relatively small band gaps that be hardly beyond 6.2 eV. Herein, a flexible π‐conjugated [C3H(CH3)O4]2− unit was theoretically revealed, showing great potential for designing NLO crystals with balanced optical properties. Accordingly, through the reasonable NLO‐favourable layered design, a new ionic organic material, NH4[LiC3H(CH3)O4], was successfully obtained. As expected, it achieves not only a large SHG effect (4×KDP), but also a suitable birefringence (0.06@546 nm) and an ultrawide band gap (>6.5 eV). This study provides a new flexible π‐conjugated NLO‐active unit, contributing to design more ionic organic NLO materials with excellent balanced optical properties.

Structural, Spectroscopic, Mechanical, and Nonlinear Optical Properties of 4-Dimethylaminopyridinium Picrate Single Crystal for Optoelectronic Applications

A novel organic nonlinear optical (NLO) material, 4-dimethylaminopyridinium picrate (4DMAPP) with molecular formula (C7H11N2)+.(C6H2N3O7)- has been synthesized. The single crystals have been grown from synthesized material by slow evaporation technique. The NLO behavior of the 4DMAPP has been investigated using the quantum chemical calculations with 6-311++G(d,p) basis set. The bond lengths, bond angles, and torsional angle of optimized structure of 4DMAPP are in good agreement with the X-ray diffraction experimental data. The global softness, electron affinity, global hardness, Ionization potential, electronegativity, global electrophilicity, and chemical potential have been estimated. The Meyer index is found to be 2.51 and the nature of the 4DMAPP NLO material is identified as soft. Thermodynamics and molecular parameters of 4DMAPP have been carried out with zero-point vibrational energy 186.191 and 171.908 kcal/mol using Hartree–Fock (HF) and density functional theory (DFT) methods, respectively. In optical absorption spectrum, the material 4DMAPP shows the lower cut off wavelength of 325 nm. The narrow energy gap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) facilitates the intramolecular charge transfer (ICT) which makes the material to be NLO active.

Third-order nonlinear response of a novel organic acetohydrazide derivative: Experimental and theoretical approach

A novel nonlinear optical (NLO) organic material of N'-[(E)-(5-bromofuran-2-yl)methylidene]-2-(6-chloropyridin-3-yl)acetohydrazide (BCA) was synthesized by reflux method. The synthesized material was characterized using various analytical techniques, including spectroscopic methods (NMR, FTIR, PXRD). The UV–Vis absorption spectrum of BCA was recorded in different solvents. A strong absorption peak was observed in the 280–350 nm range, indicating its potential for UV-based optoelectronic applications. BCA shows good NLO responses (αCT, βCT, γCTvalues) with different solvents. The dielectric measurements were performed using impedance spectroscopy with varying temperatures as a function of frequency. Thermal stability of the material was evaluated using thermogravimetric analysis, indicating high thermal stability up to 153.28°C. The FMO, MEP, and NBO analyses were implemented using density functional theory (DFT) calculations to investigate the BCA molecule's electronic structure and charge distribution. The topology studies were carried out using the QTAIM and NCI to understand the structure's chemical bonding and intermolecular interactions and the structure's chemical bonding and intermolecular interactions. NLO properties of the BCA material were investigated using the Z-scan technique with a continuous wave (CW) laser, revealing a strong third-order nonlinear susceptibility (χ(3)) value of 2.44 × 10−6 e.s.u. and potential optical limiting behavior (OL threshold = 3.437 × 103 Wcm−2). The TD-HF method performed the calculated molecular static and dynamic of NLO parameters with frequency. The computed γ value of 6.2 × 10−36 e.s.u. was found to be consistent with the experimental value. The results of this study recommend that the synthesized hydrazide derivative material has potential NLO applications.

Structural, optical, magnetic and thermal properties of L-methionine succinic acid single crystal for photonic applications

Growth and characterization of organic non-linear optical materials have accomplished tremendous standpoints whereby they perceive a wide range of applications compared to the inorganic materials because of the spectacular applications. In fact, the process of searching for potential non-linear optical materials is still in the active race even though a large number of materials have been reported over the years. In the present work, an amino acid-based single crystal of doped l-Methionine Succinic Acid (LMS) was grown by slow evaporation method at room temperature and its physio-chemical properties are reported here. The crystallographic structure and the lattice parameters of the grown crystal are studied by the Single Crystal XRD method. The undertaken UV–Visible Spectral analysis confirms that the LMS crystal is suitable for various optical applications due to its wide optical transmittance window extending throughout the visible region. The presence of the functional groups has been estimated by employing the FTIR technique. The outcome of the VSM study reveals that LMS crystal belongs to the category of soft magnetic materials.

A new benzothiazolium-based organic nonlinear optical material DABT

Second-order nonlinear optical (NLO) crystal materials are applied widely. In this work, a new benzothiazolium-based ionic organic NLO material (E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]thiazol-3-ium 4-methylbenzenesulfonate (DABT) containing strong electron donor and acceptor was designed and theoretically investigated. A simple approach that can be employed in rapidly and efficiently evaluating the second-order nonlinear properties of organic crystals based on its crystal structure information was also proposed. Results indicate that the as-designed DABT crystal possesses non-centrosymmetric structure with space group P21, and particularly, it exhibits a large static first-order hyperpolarizability of ∼117 × 10−30 esu. Moreover, the optical properties of the DABT, including its permittivity, absorption coefficient, and reflectance, were systematically investigated, revealing that the DABT crystal is an anisotropic and a new and promising material with hydrophobicity and anisotropy, holding great potential applications in nonlinear optics.

Nonlinear optical properties of symmetrical and asymmetrical benzene derivatives with click chemistry modification

PurposeThis paper aims to prepare third-order nonlinear optical (NLO) organic materials with large nonlinear optimization value, high damage threshold and ultrafast response time.Design/methodology/approachA series of novel symmetric and asymmetric compounds possessing third-order NLO properties were synthesized using 1,3,5-tribromobenzene as the basis. The photophysical and electrochemical properties, as well as the click reactions, were characterized by means of UV–VIS–NIR absorption spectroscopy and cyclic voltammetry.FindingsThe donor–acceptor chromophores were inserted into compound, making the molecule to have a broader absorption in the near-infrared regions and a narrower optical and electrochemical band gap. It also formed an electron-delocalized organic system, which has larger effects on achieving a third-order NLO response. The third-order NLO phenomenon of benzene ring complexes was experimentally studied at 532 nm using Z-scan technology, and some compounds showed the expected NLO properties.Originality/valueThe click products exhibit more NLO phenomena by performing different click combinations to the side groups, opening new perspectives on using the system in a variety of photoelectric applications.

Design, synthesis and characterization of organic second-order nonlinear optical crystal materials DOBS

Recent advance of the organic nonlinear optical (NLO) crystals on the design, synthesis and characterization of 2-(3,4-Dimethoxystyryl)-3-methylbenzothiazolium-benzenesulfonate (DOBS) is reported. It is found that crystal belongs to the triclinic system, with the space group P1. The second harmonic generation efficiency is 1.8 times higher than the standard KDP. Based on density functional theory (DFT), the maximum first-order hyperpolarizability of DOBS molecule is obtained by Gaussian calculation βmax is 107.7 × 10− 30 esu. The molecular surface electrostatic potential, HOMO-LUMO orbital, ELF/LOL, Hole-electron, Hirshfeld surface and 2-D fingerprint were analyzed. The thermal stability analysis shows that DOBS crystal has a high melting point of 251 °C. In addition, UV-Vis-NIR spectra, dielectric properties and fluorescence were investigated.

Designing Excess Electron Compounds by Substituting Alkali Metals to a Small and Versatile Tetracyclic Framework: A Theoretical Perspective.

Organic compound-based nonlinear optical (NLO) materials have sparked a lot of attention due to their multitude of applications and shorter optical response times than those of inorganic NLO materials. In the present investigation, we designed exo-exo-tetracyclo[6.2.1.13,6.02,7]dodecane (TCD) derivatives, which were obtained by replacing H atoms of methylene bridge carbon with alkali metals (Li, Na, and K). It was observed that upon the substitution of alkali metals at bridging CH2 carbon, absorption within the visible region occurred. Moving from 1 to 7 derivatives, the maximum absorption wavelength of the complexes exhibited a red shift. The designed molecules showed a high degree of intramolecular charge transfer (ICT) and excess electrons in nature, which were responsible for rapid optical response time and significant large molecular (hyper)polarizability. Calculated trends also inferred that the crucial transition energy decreased in order that also played a key role in the higher nonlinear optical response. Furthermore, to examine the effect of the structure/property relationship on the nonlinear optical properties of these investigated compounds (1-7), we calculated the density of state (DOS), transition density matrix (TDM), and frontier molecular orbitals (FMOs). The largest first static hyperpolarizability (βtot) of TCD derivative 7 was 72059 au, which was 43 times greater than that of the prototype p-nitroaniline (βtot = 1675 au).

Nanoencapsulation-Induced Second Harmonic Generation in Pillararene-Based Host-Guest Complex Cocrystals.

The features of molecularly preferable centrosymmetric arrangements exclude organic nonlinear optical (NLO) materials for second harmonic generation (SHG) when used in the solid and crystalline states, which greatly limits their applications in optoelectronic devices. Herein, a pillar[5]arene (BrP5) is used as the macrocyclic host to encapsulate NLO molecules, 4-[4'-methoxystyryl]-1-methylpyridinium iodide (OM), 4-[2'-(5'-(dimethylamino)thiophen-2'-yl)vinyl]-1-methylpyridinium iodide (DAST), and 4-methoxy-β-nitrostyrene (MNS), to alter the solid-state packing of these NLO molecules and manipulate their centrosymmetric arrangements. BrP5 forms 2:1 host-guest complexes with OM and DAST, while it forms a 1:1 host-guest complex with MNS. Experimental results show that the pillar[5]arene and each of these three NLO guests form a nanocapsule architecture along with an overall centrosymmetric crystal structure. However, the random orientation of OM and DAST molecules inside the 2:1 host-guest complex nanocapsules breaks the local centrosymmetric arrangement of the NLO molecules, resulting in strong SHG. On the contrary, for BrP5⊃MNS, the MNS molecules inside the pillar[5]arene cavities are unable to break the centrosymmetry. They have only one determined orientation in the one-dimensional (1D) channels of BrP5, while other MNS molecules in adjacent channels have the opposite direction. The centrosymmetry of the dipolar chains is strictly maintained with the cancellation of nonlinear polarization, resulting in the quenching of SHG. Furthermore, an ultrasound-induced host-guest crystallization method is developed for the fast preparation of these host-guest composite materials with NLO activity. This work opens a new way to construct solid-state organic NLO materials, which have potential in high-power lasers, optical switches, and imaging applications.