Second-order Nonlinear Optical Research Articles

Template Synthesis of Iodocuprate and Iodoargentate with Photocatalytic Activity and Second Harmonic Generation Efficiency.

In virtue of the cationic tri(pyridin-4-yl)amine (TPA) derivatives acting as the templates, two iodometallates, [Me3HTPA]2[CuI3][Cu10I16] (1) and [Me3TPA][Ag5I8] (2), were constructed with different architectures. Compound 1 features a discrete [Cu10I16]6- cluster, which is further combined with [CuI3]2- and two [Me3HTPA]4+ moieties through electrostatic interactions to result in a 3D supramolecular framework. Two types of infinite Ag-I chains with different orientations are formed in iodoargentate 2, and adjacent chains, together with in situ N-methylated cations, are further aggregated into a final 3D supramolecule. The syntheses, crystal structures, and optical properties have been studied. Notably, compound 1 displays efficient visible-light-driven photocatalytic performance for the degradation of dye pollutants. The catalytic mechanism was investigated through radical trapping experiments as well as theoretical calculations. Moreover, both the iodocuprate and iodoargentate hybrids exhibit second harmonic generation (SHG) effects, which are comparable to and even better than that of KH2PO4, indicating that the iodometallate hybrids templated by TPA-based cations could potentially serve as new candidates for second-order nonlinear optics (NLO) materials.

Exciton Enhanced Nonlinear Optical Responses in Monolayer h-BN and MoS2: Insight from First-Principles Exciton-State Coupling Formalism and Calculations.

Excitons are vital in the photophysics of materials, especially in low-dimensional systems. The conceptual and quantitative understanding of excitonic effects in nonlinear optical (NLO) processes is more challenging compared to linear ones. Here, we present an ab initio approach to second-order NLO responses, incorporating excitonic effects, that employs an exciton-state coupling formalism and allows for a detailed analysis of the role of individual excitonic states. Taking monolayer h-BN and MoS2 as two prototype 2D materials, we calculate their second harmonic generation (SHG) susceptibility and shift current conductivity tensor. We find strong excitonic enhancement in the NLO responses requires that the resonant excitons are not only optically bright themselves but also able to couple strongly to other bright excitons. Our results explain the occurrence of two strong peaks in the SHG of monolayer h-BN and why the A and B excitons of MoS2 unexpectedly exhibit minimal excitonic enhancement in both SHG and shift current generation.

Electrically switchable chiral nonlinear optics in an achiral ferroelectric 2D van der Waals halide perovskite.

Two-dimensional (2D) van der Waals (vdW) semiconductors play a key role in developing nanoscale nonlinear optical devices. 2D Ruddlesden-Popper lead halide perovskites (RPPs) expand the potential of using 2D vdW semiconductors in nonlinear optical applications because they exhibit electrically switchable and chiral second-order optical nonlinearity originating from the emergence of ferroelectricity and chirality. However, electrically switchable chiral nonlinear optics has not yet been realized because of the difficulty in electrically manipulating chiral structures. Here, we demonstrate that chiral second-harmonic generation (SHG) can be electrically induced and switched in an achiral biaxial ferroelectric 2D RPP. We observe reversible and continuous electrical switching of SHG circular dichroism and large nonlinear chiroptical activity. Polarization-resolved SHG imaging reveals that electrical poling induces the ferroelectric multidomain structure arising from the biaxial nature of the material, and the planar chirality appears. Our findings show a simple electrical control of the nonlinear chiroptical responses and establish chiral nonlinear optics based on ferroelectric 2D RPPs.

Theoretical investigation on the surrounding effects of second-order nonlinear properties for (N^C^N)Pt(II)Cl complexes

Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (1–4) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (βtot) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex 3 exhibits largest βtot value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex 3. The origin of larger βtot value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger βtot value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the βtot value in comparison with the βtot value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (μ) in contrast to the large μ value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.

InGaP χ(2) integrated photonics platform for broadband, ultra-efficient nonlinear conversion and entangled photon generation

Nonlinear optics plays an important role in many areas of science and technology. The advance of nonlinear optics is empowered by the discovery and utilization of materials with growing optical nonlinearity. Here we demonstrate an indium gallium phosphide (InGaP) integrated photonics platform for broadband, ultra-efficient second-order nonlinear optics. The InGaP nanophotonic waveguide enables second-harmonic generation with a normalized efficiency of 128, 000%/W/cm2 at 1.55 μm pump wavelength, nearly two orders of magnitude higher than the state of the art in the telecommunication C band. Further, we realize an ultra-bright, broadband time-energy entangled photon source with a pair generation rate of 97 GHz/mW and a bandwidth of 115 nm centered at the telecommunication C band. The InGaP entangled photon source shows high coincidence-to-accidental counts ratio CAR > 104 and two-photon interference visibility > 98%. The InGaP second-order nonlinear photonics platform will have wide-ranging implications for non-classical light generation, optical signal processing, and quantum networking.

Spiro-Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles.

Integration of spirocycles with buckybowls is a promising strategy to construct three-dimensional (3D) curved π-systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon-bridged spiro-type heterosumanenes (spiro-HSEs) were synthesized by combining 9,9'-spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro-conjugation plays an important role in the geometric and electronic structures of spiro-HSEs. The bowl depth of DCSs moiety becomes larger in the spiro-HSEs. Owing to the Jahn-Teller (J-T) effect, two DCSs segments of spiro-HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro-HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value-added functionalities. The emissive property is enhanced by converting the thiophene rings of S-doped spiro-HSE into thiophene S,S-dioxides. A chiroptical polycycle could be produced by ring-opening of the edge benzene of Se-doped spiro-HSE. The covalent adduct of Te-doped spiro-HSE with Br2 forms non-centrosymmetric halogen-bonded networks, resulting in the high performance second-order nonlinear optics (NLO).

DFT Study on the Second-Order NLO Responses of 2-Phenyl Benzoquinoline Ir(III) Complexes by Substituents and Redox Effects.

Metal complexes have received extensive attention in nonlinear optical (NLO) materials because of their advantages, such as shorter response times and more flexible structural properties. Density functional theory is used in investigating the geometric structures, electronic structures, charge centroid, and first hyperpolarizability (βtot) of a series of selected 15 coordinated Ir(III) complexes. The substitute effect and one-electron redox process effects on the structures and properties of 15 coordinated Ir(III) complexes are considered. When the electron-withdrawing group is introduced into the ligand, the HOMO-LUMO energy gap decreases and the βtot value increases, positively correlating with the electron-withdrawing ability. The single electron redox process can also improve the NLO responses of complexes, especially the reduction process. The βtot value of complex 4- is the largest, 2078 times higher than that of complex 4. The analysis shows that the variation of NLO responses of complexes is ascribed to the change of electronic structures and the charge transfer modes induced by the ligand modification and redox process, which are considered to be two effective methods in enhancing the NLO responses of 2-phenyl benzoquinoline Ir(III) complexes. This study aims to offer design insights into high-performance nonlinear optical materials.

Unraveling the Role of Structural Topology on Chirality Transfer and Chiroptical Properties in Chiral Germanium Iodides.

Chiral hybrid organic-inorganic metal halides are highly promising chiroptoelectronic materials with potential applications in several fields, such as circularly polarized photodetectors, second-order nonlinear optics, and spin-selective devices. However, the ability of manipulating the chiroptical response and the chirality transfer from the organic ligands require one to shed light on structure-property correlations. Herein, we devised and prepared two novel Ge-based chiral hybrid organic-inorganic metal halides showing a different structural topology, namely, a 1D and a 2D arrangement, but composed of the same chemical building blocks: (R/S-ClMBA)3GeI5 and (R/S-ClMBA)2GeI4. Through a combined experimental and computational investigation on these samples, we discuss the impact of structural dimensionality on chiroptical properties, chirality transfer, and spin-splitting effects; also, we highlight the impact of structural distortions. The approach presented here paves the way for a solid understanding of the factors affecting the properties of chiral metal halides, thus allowing a future wise materials engineering.

The effect of metal-to-ligand charge transfer on linear and nonlinear optical properties of hexaphyrin and metallo-hexaphyrins

Charge transfer from metal to ligand has implications in various fields of chemistry, physics and biology. The manipulation of spin properties would be necessary for controlling charge transfer in spintronics and biological applications. Upon binding to the metal atoms (Ni, Cu, Au, etc.), the spin properties would be modulated in organic conjugated molecules of less intrinsic spin–orbit coupling (SOC) due to SOC coming from the heavy elements. Emission spectra calculation is necessary to validate them as suitable fluorescence quenchers. The nonlinear optical properties like first-order hyperpolarisability β and second-order hyperpolarisability γ calculations are important to find out their relation between fluorescence quenching and higher order nonlinear optical (NLO) properties. From the second-order NLO properties, we computed degenerate four-wave mixing (DFWM) component ( γ ( 2 ) ( − ω ; ω , ω , − ω )) and finally quadratic nonlinear refractive indices of the expanded porphyrins (EPs). How the linear and nonlinear optical properties are dependent on the SOC coming from the heavy materials (Ni, Cu, Au), and charge transfer process is the most interesting question to be addressed for their potential uses for various optoelectronic and spintronic applications.

Exploring the ON/OFF nonlinear optical (NLO) response in tetracene-based chromophores: A DFT study on solvent and frequency-dependent NLO properties for switching applications

Tetracene-based nonlinear optical (NLO) materials are an ambient field of interest in optoelectronic technology. Inspired by this material, we theoretically designed D-D-A framework molecules (ZO and ZO-1 to ZO-16) with auxiliary donor and acceptor screening of solo tetracene linear surface and investigated their reactivity, electrical properties, solvent-dependent optical and ON/OFF NLO properties utilizing DFT simulations. The CPCM and IEFPCM model is used to examine how entire spectrum of medium polarity, ranging from less polar to more polar solvents (chloroform (ε = 4.71) < tetrahydrofuran (ε = 7.43) < DMSO (ε = 46.83 < water (ε = 78.36)) affect the optical absorption and NLO characteristics (βtot, αtot, and μtot) of suggested compounds (ZO and ZO-1 to ZO-16). Furthermore, natural bond orbital analysis (NBO) and topological analysis (MEP, ELF, and LOL) were used to explain the NLO results. Regarding the charge transfer robustness, ZO-9, a promising tetracene derivative, is identified as an appealing second-order NLO candidate, with the lowest energy gap (1.642 eV) and largest λmax (546.692 nm) among all investigated derivatives. Moreover, the solvent-dependent optical absorption spectrum shows that polar solvent (THF) alleviates the λmax from 273.081 nm to 707.511 nm in ZO-11. Similarly, solvent also influences the NLO properties in all designed compounds, especially in ZO-9, which displayed giant βtotal = 7.244 × 105 in chloroform, 8.640 × 105 in THF, 1.153 × 106 in DMSO, and 1.180 × 106 in water as well as in gas (1.993 × 105). Additionally, the results of the second harmonic generation (SHG) β(−2ω, ω, ω) and the electro-optical Pockels effect (EOPE) β(−ω,ω,0) computed at the frequencies of ω = 1064 nm (0.0428 au) and ω = 532 nm (0.0856 au) validates that all tetracene based derivatives are excellent NLO candidates for laser working condition and switching applications.

Giant nonlinear optical wave mixing in a van der Waals correlated insulator.

Optical nonlinearities are one of the most fascinating properties of two-dimensional (2D) materials. While tremendous efforts have been made to find and optimize the second-order optical nonlinearity in enormous 2D materials, opportunities to explore higher-order ones are elusive because of the much lower efficiency. Here, we report the giant high odd-order optical nonlinearities in centrosymmetric correlated van der Waals insulator manganese phosphorus triselenide. When illuminated by two near-infrared femtosecond lasers, the sample generates a series of profound four- and six-wave mixing outputs. The near-infrared third-order nonlinear susceptibility reaches near the highest record values of 2D materials. Comparative measurements to other prototypical nonlinear optical materials [lithium niobate, gallium(II) selenide, and tungsten disulfide] reveal its extraordinary wave mixing efficiency. The wave mixing processes are further used for nonlinear optical waveguide with multicolor emission. Our work highlights the promising prospect for future research of the nonlinear light-matter interactions in the correlated 2D system and for potential nonlinear photonic applications.

Second-Order Nonlinear Switching and Photoluminescence Properties of Cd-Based Hybrid Perovskite with High-Temperature Phase Transition.

Recently, organic-inorganic hybrid perovskites exhibiting facile structural phase transitions have accumulated significant attention due to their switchable second-order nonlinear optical (NLO) properties, which hold significant promise for next-generation intelligent optoelectronic devices. In this study, we present a novel one-dimensional hexagonal hybrid perovskite, (4-methoxypiperidinium)CdCl3, which undergoes a reversible high-temperature structural phase transition at 389 K. Notably, (4-methoxypiperidinium)CdCl3 demonstrates switchable second-order NLO and dielectric properties, accompanied by symmetry breaking from the centrosymmetric Pnma to noncentrosymmetric Pna21 space group. Variable-temperature structure analyses reveal that this transition is mainly driven by the order-disorder transformation of the 4-methoxypiperidinium cations. Furthermore, it also features a promising photoluminescence performance with blue-light emission and a long lifetime of 25.34 ns. It is anticipated that this study will expand the family of hybrid perovskites exhibiting high-temperature phase transitions and offer valuable guidance for the design of new NLO switching materials with superior optoelectronic properties.

Silicon Carbide Microring Resonators for Integrated Nonlinear and Quantum Photonics Based on Optical Nonlinearities

Silicon carbide (SiC) electronics has seen a rapid development in industry over the last two decades due to its capabilities in handling high powers and high temperatures while offering a high saturated carrier mobility for power electronics applications. With the increased capacity in producing large-size, single-crystalline SiC wafers, it has recently been attracting attention from academia and industry to exploit SiC for integrated photonics owing to its large bandgap energy, wide transparent window, and moderate second-order optical nonlinearity, which is absent in other centrosymmetric silicon-based material platforms. SiC with various polytypes exhibiting second- and third-order optical nonlinearities are promising for implementing nonlinear and quantum light sources in photonic integrated circuits. By optimizing the fabrication processes of the silicon carbide-on-insulator platforms, researchers have exploited the resulting high-quality-factor microring resonators for various nonlinear frequency conversions and spontaneous parametric down-conversion in photonic integrated circuits. In this paper, we review the fundamentals and applications of SiC-based microring resonators, including the material and optical properties, the device design for nonlinear and quantum light sources, the device fabrication processes, and nascent applications in integrated nonlinear and quantum photonics.

Non-covalent interaction, topology, molecular properties, spectral and quantum chemical analysis of 2,5-dinitrophenol

Density functional theory (DFT) using the Becke-3-Parameter-Lee-Yang-Parr (B3LYP) functional and Ab-initio (HF) with the 6–311++G(d,p) basis set were employed to investigate the geometry, electronic structure, and absorption spectra of 2,5-Dinitrophenol(25DNP). The vibrational spectrum was utilized to identify functional groups. The ultraviolet–visible (UV–Vis) spectrum was simulated in the gas phase using TD-DFT to determine the range and percentage of transmission. The computed HOMO and LUMO energies indicate that charge transfer occurs within the molecule. The compound exhibits a molecular first hyperpolarizability (second-order optical nonlinearity) value of 1.690 × 10−30 esu, which is approximately five times greater than that of urea. For hyperpolarizability calculations, the hybrid Hartree-Fock exchange-correlation functional was used in conjunction with the 6–311++G(d,p) basis set. Fukui indices were employed to identify local reactive sites in the chemical system during electrophilic, nucleophilic, radical, and dual descriptor attacks. Docking simulations were performed using the Lamarckian Genetic Algorithm (LGA) and local search approach, ensuring proper establishment of the ligand molecules' starting position, orientation, and torsion. According to the molecular electrostatic potential (MEP) map, positive potential sites are found around hydrogen atoms, while negative potential sites are near electronegative atoms, providing insights into regions where the molecule may interact with other molecules, both internally and externally. Similarly, Mulliken charges and Fukui indices within the organic complex sustain the intermolecular hydrogen bonds.

Tunable entangled photon-pair generation in a liquid crystal

Liquid crystals, with their ability to self-assemble, strong response to an electric field and integrability into complex systems, are key materials in light-beam manipulation1. The recently discovered ferroelectric nematic liquid crystals2,3 also have considerable second-order optical nonlinearity, making them a potential material for nonlinear optics4,5. Their use as sources of quantum light could considerably extend the boundaries of photonic quantum technologies6. However, spontaneous parametric down-conversion, the basic source of entangled photons7, heralded single photons8 and squeezed light9, has so far not been observed in liquid crystals—or in any liquids or organic materials. Here we implement spontaneous parametric down-conversion in a ferroelectric nematic liquid crystal and demonstrate electric-field tunable broadband generation of entangled photons, with an efficiency comparable to that of the best nonlinear crystals. The emission rate and polarization state of photon pairs is markedly varied by applying a few volts or twisting the molecular orientation along the sample. A liquid-crystal source enables a special type of quasi-phase matching10, which is based on the molecular twist structure and is therefore reconfigurable for the desired spectral and polarization properties of photon pairs. Such sources promise to outperform standard nonlinear optical materials in terms of functionality, brightness and the tunability of the generated quantum state. The concepts developed here can be extended to complex topological structures, macroscopic devices and multi-pixel tunable quantum light sources.

Giant nonlinear optical response of fullerene polymer fragments: a DFT perspective

Organic π-conjugated materials exhibit exceptional nonlinear optical (NLO) properties due to their unique electronic structures, characterized by short response times and large NLO responses. Fullerene (C60) is one of the few polymer species that possess a rich π-conjugated system, making it a promising material with significant NLO responses. In the present paper, we designed three C60 polymer fragments and employed density functional theory to estimate their molecular static first and second hyperpolarizabilities. Compared to previously reported fullerene derivatives, the designed C60 polymer fragments can exhibit notable second-order and third-order molecular NLO responses. The study shows that the hyperpolarizabilities and energy gaps of the investigated C60 polymer fragments are greatly influenced by their topological structures and bonding modes. These findings provide new insights for the design of novel NLO materials based on C60 polymers, and the realization of tunable NLO responses in C60 cluster-based molecular systems, which may have significant applications in nanophotonic devices.

Role of cation nature in crown ether appended 25-Oxasmaragdyrins with second-order NLO responses: As potential and selective metal ions detector

Crown ethers, known for their efficacy as metal ion traps, have garnered significant interest in optoelectronic applications due to their unique cavity structure and special binding ability with metals. Herein, we systematically designed and investigated the second-order nonlinear optical (NLO) properties of an intriguing compound, 18-crown-6 derivative appended with 25-oxasmaragdyrins (Cr-Prs), achieved through the incorporation of diverse metal ions into the crown ether ring. Significantly, the βtot values of compounds with alkaline earth metal ions (Mg2+, Ca2+) are greater than those compounds with alkali metal ions (Na+, K+). Interestingly, the Hg2+@Cr-Prs compound exhibits a tremendous second-order NLO property with the βtot value of 5.34 × 105 au. Further insights into substantial βtot values across all compounds were provided through a comprehensive analysis of the transition energies, the molecular orbitals, and the absorption spectra of the main excited states. The calculation results conclude that the second-order NLO properties of Cr-Prs can be modulated by incorporating metal ions into the crown ether ring. Crown ether emerges as a facilitator in detecting and identifying Hg2+ ions, serving as an effective NLO-based ion detector. These findings not only broaden the scope of cation detection and efficiency but also present innovative applications in analytical and optoelectronic research, encapsulating the essence of our study within a concise framework.

CMOS-compatible photonic integrated circuits on thin-film ScAlN

Scandium aluminum nitride (ScAlN) has recently emerged as an attractive material for integrated photonics due to its favorable nonlinear optical properties and compatibility with complementary metal–oxide semiconductor (CMOS) fabrication. Despite the promising and versatile material properties, it is still an outstanding challenge to realize low-loss photonic circuits on thin-film ScAlN-on-insulator wafers. Here, we present a systematic study on the material quality of sputtered thin-film Sc0.1Al0.9N produced in a CMOS-compatible 200 mm line, including its crystallinity, roughness, and second-order optical nonlinearity, and developed an optimized fabrication process to yield 400 nm thick, fully etched waveguides. With surface polishing and annealing, we achieve micro-ring resonators with an intrinsic quality factor as high as 1.47 × 105, corresponding to a propagation loss of 2.4 dB/cm. These results serve as a critical step toward developing future large-scale, low-loss photonic integrated circuits based on ScAlN.

Novel schiff base-azide metal complexes: Synthesis, spectral, nonlinear optics, and DFT studies

In order to enhance nonlinear optics (NLO)-based technologies, current research focuses on the design and synthesis of coordination materials. In this context, to investigate spectral and theoretical linear optical (LO)/nonlinear optical (NLO) behaviors, novel metal complexes including azide {[Mn (L1)2(N3)2], (9), [Ni(L1)2(N3)], (10), [Co2(L1)2(N3)2]⋅2H2O, (11); L1: N-(pyridin-2-ylmethylene)methanamine} were synthesized. The vibrational and electronic spectral features of complexes 9–11 were investigated by UV–Vis and FT–IR spectra. Depending on the central metal ion and coordination geometries of complexes, the microscopic static nonlinear behaviors were examined by using the CAM-B3LYP/and ωB97XD/6–311 + G (d,p)//LanL2DZ levels of density functional theory (DFT). Furthermore, the vibrational and electronic properties of complexes 9–11 based on the same levels of time-dependent/density functional theory (TD-DFT/DFT) were surveyed. Additionally, the theoretical χ(1), χ(2), and χ(3) parameters, known as linear optical, second-, and third-order nonlinear optical susceptibility tensors, as well as linear, second-, and third-order polarization parameters (P(1), P(2), and P(3)) for complexes 9–11 were examined. The greatest <β(0; 0,0)> value for complex 10 found to be 262.55 × 10−30 esu using CAM-B3LYP level is 820.5 and 2019.6 times higher than the urea findings (0.32 × 10−30 esu and 0.130 × 10−30 esu). The <γ(0; 0,0,0)> results indicate that complex 9 having the highest value obtained at 2216.40 × 10−36 esu using CAM-B3LYP level is 47.76 and 316.63 times greater than those of pNA (15 × 10−36 esu) and urea (7 × 10−36 esu), respectively. Complexes 10 and 9 demonstrated promising microscopic second-order and third-order NLO features, respectively. Our research is anticipated to provide insight into NLO materials that may have applications in optoelectronics and telecommunication field.

Rational design and investigation of nonlinear optical response properties of pyrrolopyrrole aza-BODIPY-based novel push-pull chromophores.

Intramolecular charge transfer (ICT)-based chromophores are highly sought after for designing near-infrared (NIR) absorbing and emitting dyes as well as for designing materials for nonlinear optical (NLO) applications. The properties of these 'push-pull' molecules can easily be modified by varying the electronic donor (D) and acceptor (A) groups as well as the π-conjugation linker. This study presents a methodical approach and employs quantum chemical analysis to explore the relationship between the structural features, electro-optical properties, and the NLO characteristics of molecules with D-π-A framework. The one- and two-photon absorption (2PA), linear polarizability (α), and first hyperpolarizability (β) of some novel chromophores, consisting of a dimeric aza-Boron Dipyrromethene (aza-BODIPY) analogue, called, pyrrolopyrrole aza-BODIPY (PPAB), serving as the acceptor, have been investigated. The electronic donors used in this study are triphenylamine (TPA) and diphenylamine (DPA), and they are conjugated to the acceptor via thienyl or phenylene π-linkers. Additionally, the Hyper-Rayleigh Scattering (βHRS), which enables direct estimation of the second-order NLO properties, is calculated for the studied chromophores with 1064 nm excitation in acetonitrile. The β value shows a significant increase with increasing solvent polarity, indicating that the ICT plays a crucial role in shaping the NLO response of the studied molecules. The enhancement of the 2PA cross-section of the investigated molecules can also be achieved by modulating the combinations of donors and linkers. The results of our study indicate that the novel D-π-A molecules designed in this work demonstrate considerably higher hyperpolarizability values than the standard p-nitroaniline, making them promising candidates for future NLO applications.