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We report on the structural, thermal, linear, and ultrafast third-order nonlinear optical (NLO) properties of two novel anthracene chalcones: (2E)-1-(anthracen-9-yl)-3-(5-methylthiophen-2-yl)prop-2-en-1-one (5ML2SANC) and (2E)-1-(9-anthryl)-3-(2,4,5-trimethoxyphenyl)prop-2-en-1-one (245TMANC). The chalcones were synthesized by Claisen-Schmidt condensation reaction, and the single crystals were grown by the solvent evaporation method. The molecular structure was confirmed by FTIR and NMR spectroscopy, while the crystal structure was determined using the single crystal XRD. Both crystals belong to centrosymmetric monoclinic crystal system with space group P21/n. The Hirshfeld surface was analyzed to understand intermolecular interactions, and the band structures - including HOMO-LUMO levels, excited state energies, GCRDs and MEPs-were studied using DFT. The ultrafast third-order NLO properties were investigated by Z-scan and degenerate four-wave mixing (DFWM) techniques using Ti: Sapphire amplifier laser delivering ∼50 fs pulses at 800 nm (1 kHz, ∼4 mJ, 2 W). Two-photon absorption, positive nonlinear refraction, optical limiting and optical switching behaviors were observed by Z-scan measurements. The time-resolved DFWM show that the decay time of 5ML2SANC is ∼127 fs, while for 245TMANC it is ∼142 fs. The second hyperpolarizability (γ) measured by Z-scan, DFWM and the estimations from the DFT theory are found to be in good agreement (∼10-34 esu). The ultrafast optical response, significant NLO properties and thermal stability of the synthesized chalcones demonstrate their potential suitability in optical limiting and switching applications.

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The nonlinear optical properties of push-pull chromophores, namely (E)-7-(4-bromophenyl)-2,5-bis(4-nitrophenyl)-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A-π-D-π-A) and (E)-7-(4-bromophenyl)-5-(4-nitrophenyl)-2-phenyl-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A-π-D-π-D), have been investigated using the z-scan technique. NMR, FT-IR, and UV-visible spectral analysis have been performed. The results were compared with density functional theory calculations employing the B3LYP/6-311++G (d, p) basis set. Geometry optimization, frontier molecular analysis, and TD-DFT calculations were conducted in various solvent environments to elucidate solute-solvent interactions. Gaussian 09 software was employed for natural bond orbital analysis, natural population analysis, and molecular electrostatic potential exploration. This comprehensive approach provides insights into the molecular structure and electronic properties of the investigated chromophores, shedding light on their potential applications in nonlinear optics. Normal coordinate analysis using the MOLVIB software has been used to assign the vibrational mode unambiguously. Theoretical second-order hyperpolarizability was computed, and NLO investigations have been employed to determine the second-order hyperpolarizability in both the polar and non-polar solvents. Further, the optical limiting capability was also examined.

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In recent years, with the rapid development of ultrastrong and ultrafast lasers, it has become essential to develop new materials with excellent nonlinear optical (NLO) properties. Porphyrin-based metal-organic frameworks (MOFs) have great potential for application in the field of NLO due to their large conjugated structure and good stability. As a typical porphyrin-based MOF, porphyrin paddle-wheel framework-3 (PPF-3) has been prepared and applied in the fields of catalysis and sensing, yet the investigation of PPF-3 in NLO remains unexplored. In this study, the ZnS/PPF-3 composite was successfully prepared using a solvent thermal method to in situ load ZnS on the surface of PPF-3. Utilizing the Z-scan technique, the NLO properties of ZnS, PPF-3, and ZnS/PPF-3 composite were investigated under different input energy intensities. ZnS/PPF-3 composite material exhibits significantly enhanced NLO properties, with the third-order nonlinear absorption coefficient (ßeff) of up to 7.00 × 10-10 m/W and a limiting threshold as low as 1.52 J/cm2, indicating its promising application potential value in the field of optical limiting. To enhance the practical utility, the ZnS/PPF-3/PVA film was prepared via the drop-casting method, achieving a maximum ßeff of 5.00 × 10-8 m/W. The smaller optical bandgap of ZnS/PPF-3 and electron transfer from PPF-3 to ZnS are the key factors that enable the ZnS/PPF-3 composite to a superior NLO performance.

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Mechanically interlocked molecules, such as rotaxanes, have drawn significant attention within supramolecular chemistry. Although a variety of macrocycles have been thoroughly explored in rotaxane synthesis, metal-organic macrocycles remain relatively under-investigated. Aluminum molecular rings, with their inner cavities and numerous binding sites, present a promising option for constructing rotaxanes. Here, we introduce an innovative "ring-donor···axle-acceptor" motif utilizing Al8 molecular rings, enabling the stepwise assembly of molecules, complexes, and polymers through tailored coordination chemistry. This novel approach can not only be applied to macrocycle-based systems like catenanes but also enhance specific functionalities progressively.

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With the wide application of laser weapons, the requirements of laser protection technology are becoming more and more strict. Therefore, it is important to find ideal optical limiting (OL) materials to protect human eyes and detectors. In this work, the nonlinear optical responses of gold nanoparticles/porous carbon (Au NPs/PC) nanocomposites prepared by the reduction method were studied using the nanosecond Z-scan technique. Compared with porous carbon, the Au NPs/PC nanocomposites show a lower damage threshold, a bigger optical limiting index and a wider absorption spectrum. The interaction between gold nanoparticles and porous carbon enhances the nonlinear scattering effect of suspended bubbles. These results indicate that Au NPs composites have potential applications in the protection of human eyes and detectors.

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Graphene Quantum Dots (GQDs) are crucial in biomedicine for sensitive biosensing and high-resolution bioimaging and in photonics for their nonlinear optical properties. Integrating GQDs with photonic structures enhances optical properties by optimizing light-matter interactions and enabling precise control over their emission wavelengths. In this work, we explore a facile synthesis method for GQDs by pulsed laser irradiation in chlorobenzene and highlight the transformative potential of Tamm Plasmon Cavity (TPC) structures for tuning and amplifying the photoluminescence and nonlinear optical properties of GQDs. The characterization of GQDs revealed their exceptional properties, including efficient optical limiting and stable photoluminescence. The study demonstrated that the TPC structure significantly amplifies nonlinear optical effects due to the high light-matter interaction, indicating the potential for advanced optical systems, including optical limiters and nonlinear optical devices. Furthermore, introducing GQDs into the TPC structure leads to a significant enhancement and tuning of fluorescence emission. The Purcell effect, in combination with the confined electromagnetic fields within the TPC, increases the spontaneous emission rate of GQDs and subsequently enhances the fluorescence intensity. This enhanced and tunable fluorescence has exciting implications for high-sensitivity applications such as biosensing and single-molecule detection.

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With the wide application of intense lasers, the protection of human eyes and detectors from laser damage is becoming more and more strict. In this paper, we study the nonlinear optical limiting (OL) properties of porous carbon with a super large specific surface area (2.9 × 103 m2/g) using the nanosecond Z-scan technique. Compared to the traditional OL material C60, the porous carbon material shows an excellent broadband limiting effect, and the limiting thresholds correspond to 0.11 J/cm2 for 532 nm and 0.25 J/cm2 for 1064 nm pulses, respectively. The nonlinear scattering experiments showed that the OL behavior was mainly attributed to the nonlinear scattering effect, which is caused by the rapid growth and expansion of bubbles in the dispersion induced by laser irradiation, and the scattered light distribution is consistent with the results of Mie's scattering. These results suggest that porous carbon materials are expected to be applied to the field of laser protection in the future to further protect the human eye and precision optical instruments.

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Although laser technology brings convenience to production and daily life, it also causes high-energy damage. Therefore, there is an urgent need to develop optical limiting materials for laser protection. In this study, a novel nonlinear optical material, red/black phosphorus lateral heterojunction, is successfully prepared through solvothermal and ultrasonic treatment. Using the Z-scan method, the nonlinear optical properties of the red/black phosphorus heterojunction are determined at wavelengths of 532 and 1064 nm. These results indicate that the red/black phosphorus heterojunction exhibits reverse saturable absorption properties in 1.2.3-glycerol. Interestingly, the red/black phosphorus heterojunction shows an enhanced performance over red phosphorus by introducing the black phosphorus phase. Moreover, the red/black phosphorus heterojunction is doped into organically modified silicate gel glass with excellent broadband optical limiting performance. This study highlights the promising prospect of the red/black phosphorus heterojunction in the nonlinear optical and optical limiting fields.

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There is a mounting demand for nonlinear optical materials with superior optical limiting performance which has a noticeable impact on protecting the delicate optical components from laser-induced damage. Transition metal molybdates have garnered attention in the nonlinear optics field due to their outstanding optical and luminescent properties, which give rise to widespread applications in next-generation optoelectronics devices. The structural confirmation of the as prepared silver molybdate nanoparticles were made by XRD and Raman spectroscopy analysis. The linear optical properties and the band gap of the synthesized material were studied using UV-Visible and photoluminescence spectroscopy. SEM analysis revealed the pebble like morphology of the silver molybdate nanostructures. The nonlinear responses of the samples were studied using open aperture z-scan approach with Nd:YAG pulsed laser (532 nm, 9 ns, 10 Hz). The sample exhibits reverse saturable absorption pattern attributed to the two photon absorption (2PA) mechanism. The obtained OL threshold value is in the order of 1012 which is suitable for fabricating optical limiters in nano second pulsed laser regime.

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N-S codoped TiO2 nanoparticles (NPs) were synthesized using a sol-gel cum hydrothermal approach, with ammonium sulfate as the nitrogen and sulfur source compound. The calcination temperature was varied from 500 to 700 °C. The pristine samples exhibited a mixed phase of anatase and brookite, while the doped samples exhibited only the anatase phase, as confirmed by X-ray diffraction (XRD) analysis. Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of N-H vibrations and S-O bidentate complexation with Ti4+ ions. Electron paramagnetic resonance (EPR) revealed the presence of Ti3+ signals, confirming the creation of oxygen defects in the doped samples. The absorption and emission properties of the samples were investigated using ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy. Vibrating sample magnetometry (VSM) analysis confirms the room-temperature ferromagnetic behavior of the N-S doped TiO2, which was attributed to the presence of oxygen vacancies, as evidenced by the EPR and PL results. The N-S doped TiO2 samples demonstrated superior photocatalytic degradation of Rhodamine B (RhB), Methylene Blue (MB), and Congo Red (CR) dyes under visible light illumination compared to the pristine TiO2. This enhanced performance was attributed to the presence of N and S dopants in TiO2, which create new energy levels within the band structure of TiO2, allowing for efficient absorption of visible light and subsequent generation of reactive species for dye degradation. N-S doping modifies the electronic structure of TiO2, enhancing two-photon absorption (TPA). This increased TPA efficiency suggests promising applications in optical devices, such as laser protection systems and optical limiters. Density Functional Theory (DFT) investigation also confirms that the presence of oxygen vacancies generates energy states below the conduction band. This, in turn, benefits the absorption of more visible light during photocatalytic activities and leads to a notable nonlinear absorption in optical limiting. Overall, the N-S doping strategy significantly improves the photocatalytic and optical limiting performance of TiO2 NPs, making them promising candidates for a wide range of applications.

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Crystal-liquid-glass, which combines the tunable properties of crystalline compounds with the processability of glasses, has emerged as a new class of materials for fabricating bulk-shapable devices in real applications. Inspired by the characteristics of deep eutectic solvent (DES) mixtures involving significant depressions in melting points compared to their neat constituent components, in this study, we designed and synthesized the first examples of meltable aluminum oxo clusters (AlOCs) via lattice doping with DESs at the molecular level. The abundant and strong hydrogen bonding between the aluminum molecular ring, DES components, and lattice solvents is postulated to be the root that affords melting point depressions and, thus, "melting" clusters. We prepared a transparent bubble-free glass film under autogenous pressure using a hot-press method. These cluster-based films exhibited luminescent and nonlinear optical properties similar to those of pristine crystalline compounds. Our study belongs to the interdisciplinary disciplines of chemistry and physics. It not only breaks the limitations of crystalline glass on metal and ligand types but also acts as a general guide for extending the range of meltable crystalline materials.

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Herein, we report the extraction of natural pigment curcumin from curcuma longa and their linear and third-order nonlinear optical (NLO) characteristics. The characterization techniques viz., UV-Visible absorption, FT-IR, Micro Raman and Gas Chromatography Mass Spectrum (GC-MS) are used to study the spectral characteristics of curcumin. Third-order NLO features of curcumin are studied using Z‒scan technique with a semiconductor diode laser working at 405 nm wavelength. The natural pigment exhibits negative nonlinear index of refraction resulting from self-defocusing and positive coefficient of absorption is the consequence of reverse saturable absorption (RSA). The order of nonlinear index of refraction (n2) and nonlinear coefficient of absorption (ß) is measured to be 10-7 cm2/W and 10-2 cm/W, respectively. Third-order NLO susceptibility (χ(3)) and second-order hyperpolarizability (γ) of curcumin is measured to be 2.73 × 10‒7 esu and 1.67 × 10‒31 esu, respectively. A low optical limiting (OL) threshold of 0.71 mW is observed in the extracted pigment. The experimental results are supplemented by quantum mechanical calculations of the NLO parameters. The overall result finding is that curcumin extracted from curcuma longa has the potential to be novel optical candidates for photonics and optoelectronics applications.

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In this work, the optical limiting response of a highly π-conjugated push-pull chalcone derivative (2E)-3-(2,3-dimethoxyphenyl)-1-(3-nitrophenyl)prop-2-en-1-one (abbreviated as 3DPNP) has been investigated. The structure-property relationship of 3DPNP was explored through spectroscopic investigation and quantum chemical computations. The existence of weak-non-covalent interactions and charge transfer species that responsible for the chemical stability of 3DPNP were studied by AIM and NBO analyses. The quantitative and qualitative analysis of vibrational and electronic contribution to non-linear optical (NLO) response of 3DPNP were discussed in detail. The normal vibrational modes associated with a change in the dipole moment, polarizability, first- and second-order hyperpolarizabilities of 3DPNP were identified using DFT calculations followed by potential energy distribution (PED) analysis using Gaussian 09 W software and Gar2ped program, respectively. The changes in the NLO parameters with respect to the varying frequencies and electric dipole fields were studied. The abrupt changes in the NLO properties were noticed when the frequency doubled, confirming the second harmonic generation (SHG) efficiency of 3DPNP. From the non-linear absorption and refraction studies through the z-scan experiment, the optical limiting threshold value of 3DPNP is determined to be 3.26 kJ/cm2, which shows the suitability of the material for optical limiting applications in the continuous wave (CW) laser regime.

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Recently, the preparation of some hematene and magnetene ultrathin non van der Waals (non-vdW) 2D nanoplatelets was reported starting from hematite and magnetite natural iron ores. The present work reports on the determination and evaluation of the nonlinear optical response and the optical limiting (OL) action of these 2D nanoplatelets dispersed in water under ns laser excitation. The obtained results show that both hematene and magnetene exhibit strong nonlinear absorption and refraction, comparable and even larger than those of other van der Waals (vdW) 2D counterpart materials. In addition, due to their strong nonlinear absorption, both hematene and magnetene show exceptional OL performance from the UV to visible, attaining very low values of optical limiting onset (OLon ), comparable and even lower than that of vdW 2D nanomaterials, such as graphene, graphene oxide, other transition metal dichalcogenides like MoS2 , WS2 and MoSe2 , black phosphorous and antimonene. Moreover, hematene was found to exhibit more efficient OL action than magnetene for all the excitation wavelengths studied, attributed to more efficient ligand to metal charge transfer. The present findings open new possibilities for the potential use of these non-vdW 2D materials in photonics and optoelectronics, e. g., as optical limiters and optical switchers.

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Selenium (Se) is located in the fourth period of the periodic table in group VIA (element 34). In this experiment, three different solvents (isopropyl alcohol, N-methyl-2-pyrrolidone, and ethanol) were used to prepare the two-dimensional Se nanosheets, which were manufactured by the liquid phase exfoliation method with a thickness of 3.35-4.64 nm and a transverse scale of several hundred nanometers. The nonlinear absorption properties at 355, 532, and 1064 nm were studied using the open apertureZ-scan technique. Final results showed that Se nanosheets exhibited optical limiting (OL) effect in all three wavebands and three solvents, and had large two-photon absorption coefficients, especially in ultraviolet (UV) waveband. Which proved that Se nanosheets had great potential application as excellent OL materials in UV waveband. Our research broadens the path for the semiconductor field of Se, inspires the application of Se in nonlinear optics field.

Asunto(s)

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In recent years, boron nitride nanomaterials have attracted increasing attention due to their unique properties such as high temperature stability and high thermal conductivity. They are structurally analogous to carbon nanomaterials and can also be generated as zero-dimensional nanoparticles and fullerenes, one-dimensional nanotubes and nanoribbons, and two-dimensional nanosheets or platelets. In contrast to carbon-based nanomaterials, which have been extensively studied during recent years, the optical limiting properties of boron nitride nanomaterials have hardly been analysed so far. This work summarises a comprehensive study on the nonlinear optical response of dispersed boron nitride nanotubes, boron nitride nanoplatelets, and boron nitride nanoparticles using nanosecond laser pulses at 532 nm. Their optical limiting behaviour is characterised by means of nonlinear transmittance and scattered energy measurements and a beam profiling camera is used to analyse the beam characteristics of the transmitted laser radiation. Our results show that nonlinear scattering dominates the OL performance of all measured boron nitride nanomaterials. Boron nitride nanotubes show a large optical limiting effect, much stronger than the benchmark material, multi-walled carbon nanotubes, which makes them promising for laser protection applications.

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Structural asymmetry affecting the nonlinear optics (NLO) of metal-organic frameworks (MOFs) is very important in fundamentals and applications but is still a challenge. Herein we develop a series of indium-porphyrinic framework (InTCPP) thin films and provide the first study on the coordination-induced symmetry breaking on their third-order NLO. The continuous and oriented InTCPP(H2) thin films were grown on quartz substrates and then postcoordinated with different cations (Fe2+ or Fe3+Cl-) in InTCPP(H2) (named InTCPP(Fe2+) and InTCPP(Fe3+Cl-)). The third-order NLO results reveal the Fe2+ and Fe3+Cl- coordinated InTCPP thin films have substantially enhanced NLO performance. Moreover, InTCPP(Fe3+Cl-) thin films cause symmetry breaking of microstructures, resulting in a 3-fold increase in the nonlinear absorption coefficient (up to 6.35 × 10-6 m/W) compared to InTCPP(Fe2+). This work not only develops a series of nonlinear optical MOF thin films but also provides new insight into symmetry breaking on MOFs for nonlinear optoelectronic applications.

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With the development of laser technology, the research of novel laser protection materials is of great significance. In this work, dispersible siloxene nanosheets (SiNSs) with a thickness of about 1.5 nm are prepared by the top-down topological reaction method. Based on the Z-scan and optical limiting testing under the visible-near IR ranges nanosecond laser, the broad-band nonlinear optical properties of the SiNSs and their hybrid gel glasses are investigated. The results show that the SiNSs have outstanding nonlinear optical properties. Meanwhile, the SiNSs hybrid gel glasses also exhibit high transmittance and excellent optical limiting capabilities. It demonstrates that SiNSs are promising materials for broad-band nonlinear optical limiting and even have potential applications in optoelectronics.

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A helicene-containing arene and its linear analogue have been successfully synthesized and characterized, where the single-crystal X-ray diffraction analysis indicates that the former can arrange in an offset packing style with a π-π overlap. The introduction of pentagon-rings into the parent skeletons in the resulting compounds can boost the stability, and such helicene-containing molecule possesses higher solubility in organic solvent than the linear analogue. The structural difference has significantly influenced the optical limiting performance. The former in solution and in doped gel glass presents higher optical limiting response towards 532 nm laser than the latter. This study can enrich the functionalization of helicene, which can possess a positive effect in terms of nonlinear optical property.

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The vastness of organic synthetic strategies and knowledge of reticular chemistry have made covalent organic frameworks (COFs) one of the most chemically and structurally diverse class of materials with potential applications ranging from gas storage, molecular separation, and catalysis to energy storage and magnetism. Recently, this class of porous materials has garnered increasing interest as potential nonlinear optical (NLO) materials. Traditionally, inorganic crystals, small-molecule organic chromophores, and oligomers have been studied for their NLO response. Nevertheless, COFs offer significant advantages over existing NLO materials in terms of higher mechanical strength, thermochemical stability, and extended conjugation. Herein, we discuss crucial aspects, terminology, and measurement techniques related to NLO, followed by a critical analysis of the design principles for COFs with NLO response. Furthermore, we touch on selected potential applications of these NLO materials. Finally, future prospects and challenges of COFs as NLO materials are discussed.