Mercaptopyridine-substituted indium,zinc, and metal-free phthalocyanines: nonlinear optical studies in solution and on polymer matrices

In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl₃, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10^?9 esu and 7.74 × 10^?10 esu) and hyperpolarizability (2.13 × 10^?28 and 8.37 × 10^?29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters.     

Preparation and nonlinear optical properties of Au nanoparticles doped TiO2 thin films

Nano-sized noble metal nanoparticles doped dielectric composite films with large third-order nonlinear susceptibility due to the confinement and the enhancement of local field were considered to be applied for optical information processing devices, such as optical switch or all optical logical gates. In this paper, sol–gel titania thin films doped with gold nanoparticles (AuNPs, ~10 nm in average size) were prepared. AuNPs were firstly synthesized from HAuCl₄ in aqueous solution at ~60 °C, using trisodium citrate as the reducing agent, polyvinylpyrrolidone as the stable agent; then the particle size and optical absorption spectra of the AuNPs in aqueous solutions were characterized by transmitting electron microscopy and UV–Vis–NIR spectrometry. Sol–gel 2AuNPs–100TiO₂ (in %mol) thin films (5 layers, ~1 μm in thickness) were deposited on silica glass slides by multilayer dip-coating. After heat-treated at 300–1,000 °C in air, the AuNPs–TiO₂ thin films were investigated by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The nonlinear optical properties of the AuNPs–TiO₂ thin films were measured with the Z-scan technique, using a femtosecond laser (200 fs) at the wavelength of 800 nm. The third-order nonlinear refractive index and nonlinear absorption coefficient of 2AuNPs–100TiO₂ films were at the order of 10^?12 cm²/W, and the order of 10^?6 cm/W, respectively, and the third-order optical nonlinear susceptibility χ⁽³⁾ was ~6.88 × 10^?10 esu.     

Calculation of the nonlinear electric susceptibility of benzene

We calculate the various components of the third-order nonlinear electric susceptibility of the benzene molecule, starting from a CNDO wavefunction. Our theoretical result for the space-fixed nonlinear third-order susceptibility is 6.15 × 10^?36 esu, the corresponding experimental value is 1.58 × 10^?36 esu. We also estimate the contributions from the σ and π electrons to the total susceptibility.     

Structures and enhanced third-order nonlinear optical performance of four complexes investigated by thin film <Emphasis Type="Italic">Z-</Emphasis>scan technique

Four transition metal complexes have been synthesized via hydrothermal reactions, namely, [Zn(1,3-BIB)(CH₃COO)₂]₂ 1, [Cu₂(1,4-BIB)₃(CO₃)₂](1,4-BIB)·10H₂O 2, {[Mn(H₂O)₂(1,2-BIB)₂]Cl₂}_n 3, and {[Mn(1,2-BIB)(1,4-NDC)]₂}_n 4, where 1,n-BIB = 1,n-bis(imidazol-l-yl-methyl)benzene, n = 2, 3, 4 and 1,4-NDC = naphthalene-1,4-dicarboxylic acid. Complex 1 presents a discrete ring-like structure. Complex 2 shows a ladder-like chain structure, while complex 3 has a joint-like chain structure. Complex 4 features a layer structure constructed from [Mn₂(N₄O₈)] clusters. The third-order nonlinear optical (NLO) properties of these complexes in thin films have been investigated by employing the Z-scan technique. Complexes 1–3 exhibit strong third-order NLO reverse-saturable absorption, while 4 shows third-order NLO saturable absorption and a strong self-defocusing effect. The third-order NLO susceptibilities χ ⁽³⁾ of the four complexes were calculated as 2.74 × 10^?9, 12.24 × 10^?9, 42.78 × 10^?9 and 189.32 × 10^?9 esu, respectively. The electronic structures of the complexes were investigated by density functional theory, and the origins of their NLO properties are discussed.     

A theoretical investigation of intermolecular interaction of a phthalimide based “on–off” sensor with different halide ions: tuning its efficiency and electro-optical properties

The interaction between chemosensor, N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (1) and different halide ions (F ^? , Cl^? and Br^?) has been investigated using density functional theory (DFT). A clear insight of the sensor anion binding process has been presented. Our calculations revealed that the observed colorimetric and fluorescent signals are induced due to the ground state deprotonation of the sensor molecule caused by F^? which has two times higher binding affinity than other halide ions (Cl^? and Br^?). Derivatives of system 1 have been made to find a better sensor with higher binding affinity and longer wavelength of absorption. All the derivatives are better sensors than the parent 1 except 4-methyl-N-(2-methyl-1,3-dioxo-indan-5-yl)-benzamide (2). Among these derivatives, trimethyl-[4-(2-methyl-1,3-dioxo-indan-5-ylcarbamoyl)-phenyl]-ammonium (8) and (5-benzoylamino-1,3-dioxo-indan-2-yl)-trimethyl-ammonium (9) showed a change to higher binding energies of about 58 Kcal/mol and longer absorption wavelengths of 53 nm after deprotonation process than the parent system 1 which is highly demanded in selective chemical sensing. Systems 8, 9 and their deprotonated zwitterionic forms (8z and 9z) have also been studied for their nonlinear optical responses. Systems 8, 9 showed significantly good first hyperpolarizability (β) of 84 × 10^?30 and 40 × 10^?30 esu, respectively. These β values increase in zwitterionic states up to 216 × 10^?30 and 109 × 10^?30 esu, respectively after deprotonation with F^?, representing a new signal of deprotonation.     

Third-order Nonlinear Optical Properties of Octa-substituted Metal-free Phthalocyanine Thin Films

Third-order nonlinear optical susceptibility, χ⁽³⁾ of symmetrically octa-substituted metal-free phthalocyanine thin films measured by the third-harmonic generation technique are reported. The metal-free phthalocyanine has been found to show a χ⁽³⁾ (−3ω; ω,ω, ω) value as large as 7.73×10⁻¹² esu at 1.80 μm. The figure of merit, χ⁽³⁾/α, was estimated to be 4.17×10¹⁷ esu cm at 1.05 μm and 6.97×10¹⁶ esu cm at 1.65 μm. Both linear and third-order optical properties of liquid-crystalline metal-free phthalocyanines are discussed     

Ultrafast nonlinear optical response of Ag nanoparticles embedded in mesoporous thin films

Highly dispersed silver nanoparticles embedded in mesoporous thin films (MTFs) have been synthesized by modification of the interior surface of mesoporous silica with ethylenediamine moieties, which provided the coordination sites for the Ag ions, and subsequent reduction under hydrogen atmosphere. TEM observations show the mesoporous parent films have effectively controlled the growth of the synthesized silver nanoparticles. The composite films had an ultrafast nonlinear response time, as fast as 200 fs, and a third-order nonlinear optical susceptibility of 0.94 × 10^?10 esu, which was enhanced by the local field enhancement effect that was present when the silver nanoparticles were embedded in the surrounding dielectric matrix. The origin of the ultrafast nonlinear response and the enhanced nonlinearity of the composite films are attributed to the intraband transition of the free electrons near the Fermi surface of the incorporated silver nanoparticles.     

Synthesis and Third‐Order Nonlinear Optical Properties of Triphenylene Derivatives Modified by Click Chemistry

A series of asymmetric triphenylene derivatives containing typical D –π–A structures is successfully synthesized by means of [2+2] cycloaddition–cycloreversion click reactions. The photophysical and electrochemical properties, as well as the click reactions, are characterized by means of UV/Vis absorption spectroscopy, cyclic voltammetry, and DFT modulations. In addition, the third‐order nonlinear properties, including the nonlinear absorption and the nonlinear susceptibilities, are investigated by using Z‐scan techniques. A typical reverse saturable absorption–saturable absorption behavior is observed for the third‐order nonlinear absorption, with the third‐order nonlinear susceptibilities of the compounds being 1.05×10^?12, ?1.50×10^?12, and ?0.52×10^?12 esu, respectively.     

Influence of acceptor tethering on the performance of nonlinear optical properties for pyrene-based materials with A-π-D-π-D architecture

In this study, we designed a series of pyrene-based donor-π-donor-π-acceptor compounds (HPTC1-HPTC7) by structural tailoring the reference compound (HPTC) using acceptor units. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), natural bonding orbital (NBO), transition density matric (TDM) analysis, and absorption spectra of reference and proposed derivatives were calculated at M06/6-31G(d,p) functional. All the designed compounds have smaller energy bandgaps than the HPTC compound. Moreover, the designed compounds exhibited larger global softness values than the reference. The absorption maxima of HPTC2, HPTC3, and HPTC7 are blue shifted with respect to HPTC. NBO analysis revealed that prolonged hyper conjugative associations and strong interactions between the donor (π) and acceptor (π*) moieties play a crucial part in their stabilization. The FMO and NBO findings supported the NLO responses of entitled compounds, and consequently, the linear and nonlinear properties of designed derivatives elevate compared to the reference molecule. Promisingly, the NLO response for HPTC7 comprises of highest values of <α>, β_total and < γ > as 1.92 × 10^?22 esu, 1.95 × 10^?27 esu, and 4.69 × 10⁷ (a.u). This NLO behavior shows push–pull NLO chromophores for HPTC7 predicting its role in pursuing NLO materials for optoelectronic applications.     

Synthesis and characterization of photorefractive polymers containing indole groups

Some new photorefractive polymers containing indole groups were synthesized and characterized by IR, ¹H NMR, and UV techniques. The Gibbs free energy changes (ΔG) of corresponding reactions were predicted by density functional theory to be 4.19 and ?9.71 kcal mol^?1 for –H, and 4.12 and ?11.93 kcal mol^?1 for –OCH₃, respectively. The glass transition temperature (T _g) of the polymers were about 96–111 °C. The nonlinear second-order optical susceptibility was predicted to be 2.84 × 10^?30 and 1.04 × 10^?30 esu by theoretical quantum calculations.     

Synthesis,crystal structure,and third-order non-linear optical properties of a new Cd(II) polymer constructed from pyrazine-2-carboxylic acid

A new cadmium(II) pyrazine-2-carboxylate coordination polymer, {[Cd(L)(H₂O)₂(SO₄)_0.5]₂·H₂O}_n (1) (HL = pyrazine-2-carboxylic acid), has been synthesized by low-temperature solid-state reaction. Single-crystal X-ray analyses reveal that 1 possesses a 3-D framework structure. The polymer 1 was characterized by elemental analyses, thermogravimetric analyses, X-ray powder diffraction analyses, IR spectra, and UV–visible spectra. The third-order non-linear optical properties were also investigated and they exhibit nice non-linear absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 1.30 × 10^?30 esu for 1 in a 2.01 × 10^?4 M?dm^?3 DMF solution.     

Design and synthesis of polyindole - ZnO nano composite for NLO applications

Present paper mainly focuses on the synthesis, characterization polyindole-ZnO nano composites for third order nonlinear optical applications. Polyindole was synthesized through oxidative polymerization technique and its composites were prepared with different ZnO concentration. Structural morphology of the polymer composite was studied using FESEM, XRD and UV Visible spectroscopic technique. Polymer showed broad absorption with absorption maxima of 395 nm. Newly prepared thin films showed excellent nonlinear absorption with very good optical limiting behaviour when it is exposed to He-Ne laser with maximum optical limiting power of 11 mW along with third-order nonlinear susceptibility χ⁽³⁾ of 2.72 × 10^?3 esu. Hence these polymer composites may be potential candidate for optical limiting applications.     

Synthesis and property of soluble poly(1,1′-dialkyl-3,3′-ferrocenylenevinylene)s via titanium-induced dicarbonyl-coupling reaction of 1,1′-dialkylferrocene-3,3′-dicarbaldehydes

1,1′-Dialkylferrocene-3,3′-dicarbaldehydes ( 1a–c ) with long alkyl chains such as ethyl, hexyl, and dodecyl groups were prepared in 13–25% yield via three-step reactions. The titanium-induced dicarbonyl-coupling reaction of 1a–c gave poly(1,1′-dialkyl-3,3′-ferrocenylenevi-nylene)s ( 2a–c ) in quantitative yields, which were the molecular weights of 3000–10,000 and highly soluble in chloroform, benzene, and hexane. The electrical conductivity and the third-order nonlinear optical susceptibility for poly(1,1′-dihexyl-3,3′-ferrocenylenevinylene) ( 2b ) were estimated to be 1 × 10^?2 S/cm on doping with iodine and 1–4 × 10^?12 esu at a wavelength of 1–2.4 μm, respectively. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of novel second-order NLO-chromophores bearing pyrrole as an electron donor group

Two series of novel push–pull 1-(4-(thiophen-2-yl)phenyl)-1H-pyrroles 3–5 were designed to explore the consequence of using different electron accepting moieties linked to the thiophene at the arylthiophene bridge or to the pyrrole heterocycle, which plays the role of donor group. Compound 2 showed a different reactivity behavior in the presence of the Vilsmeier reagent or with tetracyanoethylene (TCNE) giving compounds 4a and 4b functionalized, respectively, at the 2 or on the 3-position of the pyrrole heterocycle. Their optical (linear and first hyperpolarizability), electrochemical, and thermal properties have been examined. Hyper-Rayleigh scattering (HRS) in dioxane solutions using a fundamental wavelength of 1064 nm was employed to evaluate their second-order nonlinear optical properties. Of these systems, thiobarbituric acid derivative 5b functionalized in the thiophene ring exhibits the largest first hyperpolarizability (β=2480×10^?30 esu, T convention) compared to the corresponding compound 4c substituted on the pyrrole heterocycle (β=290×10^?30 esu, T convention). Good to excellent thermal stabilities were also obtained for push–pull compounds 4 and 5 (270–288 °C). This multidisciplinary study shows that modulation of the optical and electronic properties can be achieved by introduction of the acceptor groups in the thiophene of the arylthiophene bridge. The measured molecular first hyperpolarizabilities and the observed electrochemical behavior are quite sensitive to the position of acceptor group on the heterocyclic system (on the thiophene or on the pyrrole ring) as well as the strength of the acceptor moieties. Moreover, the combination of their good nonlinearity and high thermal stability make them good candidates for second-order nonlinear optical applications.     

Measurements of light scattering changes induced by a strong optical field in solutions of tRNA

Changes in light scattering induced by a strong laser beam, as predicted theoretically by Kielich, were measured for unfractionated yeast transfer ribonucleic acid (tRNA) solutions. The vertically polarized electric field of a strong laser pulse (λ = 1060nm) amounted to 4.5 × 10³ esu cgs; its duration was 10 nsec. A weak incident laser beam (λ = 630nm) was also polarized vertically and the vertical and horizontal intensity components of the light scattered through 90° at the latter wavelength were measured. These measurements together with previous results from measurements of Rayleigh light scattering and light scattering in a magnetic field permitted evaluation of the tensor of third-order polarizability (c = 3 × 10^?30 esu cgs, c = ?373 × 10^?30 esu cgs) and the anisotropy of the third-order polarizability components with its sign (δ_c = +56 × 10^?2, δ_c = +0.25 × 10^?2 for tRNA monomer and aggregate, respectively). The new method described may be useful for studies of macromolecules and macromolecular complexes of biological importance.     

四叔丁基萘酞菁铅化合物的非线性和光限幅特性

合成了四叔丁基萘酞菁铅[(t-Bu)₄NcPb]化合物. 利用元素分析、红外光谱、核磁共振氢谱等方法, 验证了化合物的分子结构. 应用调Q倍频ns/ps Nd:YAG脉冲激光系统, 在波长为532 nm下, 研究了化合物的非线性和光限幅特性. 测得化合物的非线性折射率n₂和三阶非线性极化率χ⁽³⁾分别为2.42×10^－11和7.91×10^－12 esu, 通过计算得到分子极化率γ'为3.4×10^－29 esu. 在透过率69%时限幅阈值为1522 mJ/cm², 箝位值为553 mJ/cm², 有效激发态与基态吸收截面比为3.16.     

Study of Linear and Nonlinear Optical Properties of Four Derivatives of Substituted Aryl Hydrazones of 1,8‐Naphthalimide

Four 1,8‐naphthalimide hydrazone molecules with different electron‐donating groups have been applied in the study of linear and nonlinear optical (NLO) properties. These compounds showed strong green emission in solution. Their NLO properties such as two‐photon absorption (TPA) behavior with femtosecond laser pulses ca. 800 nm and excited‐state absorption (ESA) behavior with nanosecond laser pulses at 532 nm were investigated. Compound 4 presented the largest two‐photon cross section (550 GM) among them due to two factors: the conjugated length of compound 4 is the longest and the electron‐donating ability of compound 4 is the strongest. Different from TPA behavior, compound 2 showed the best nonlinear absorption properties at 532 nm and its nonlinear absorption coefficient and third‐order nonlinear optical susceptibilities χ ⁽³⁾ were up to 1.41×10^?10 MKS and 4.65×10^?12 esu, respectively. Through the modification of the structure, the nonlinear optical properties of these compounds at different wavelengths (532 and 800 nm) were well tuned. The great broad‐band nonlinear optical properties indicate hydrazones are good candidates for organic nonlinear optical absorption materials.     

Non‐Resonant z‐Scan Characterization of the Third‐Order Nonlinear Optical Properties of Conjugated Poly(thiophene azines)

The nonlinear optical properties of a functionalized poly(thiophene azine), namely, poly(3,4‐didodecylthiophene azine), PAZ, at the optical telecommunication wavelength of 1550 nm are investigated by means of the closed‐aperture z‐scan technique in both thin films and solutions. Values of χ⁽³⁾=(2.4±0.4)×10^?13 esu, n₂=(4.0±0.7)×10^?15 cm² W^?1, and γ=(4.5±0.7)×10^?34 esu are estimated for the third‐order (Kerr) susceptibility, the intensity‐dependent refractive index, and the molecular second hyperpolarizability of solution samples, respectively. A very small dependence on the polymer chain length is found. Markedly higher values of (4.4±1.1)×10^?11 esu, (6.6±1.0)×10^?13 cm² W^?1, and (5.0±0.8)×10^?33 esu are measured for the corresponding quantities in thick (up to 20 μm) polymer films cast on quartz plates. The enhancement of the NLO responses on going from solution to solid samples is attributed to a partially ordered structure and to the presence of interchain interactions leading to greater π‐electron delocalization in the cast polymer films. The results are compared with those previously obtained by using third‐harmonic generation (THG), taking into account that those data were measured under conditions of three‐photon resonance, whereas our z‐scan measurements are fully off‐resonance.     

Study of third-order nonlinear susceptibility of polySchiff base containing triphenylamine

PolySchiff base containing triphenylamine has been synthesized by polycondensation and character-ized by FT-IR,NMR,UV-visible spectrometer. Measurements of the third-order optical nonlinear sus-ceptibility χ(3) by Z-scan technique have shown that the large nonlinearity is dominated by the two-photon absorption in PSB. The sign and size of real part Reχ(3) ,nonlinear refractive index n2 have been measured with the condition of 532 nm,8 ns-duration pulses to be -1.23×10-10 esu,-3.06×10-12 esu;nonlinear absorption index β and size of image part Imχ(3) to be 3.63×10-10 m/W,1.15×10-11 esu,respec-tively,so the third-order nonlinear susceptibility χ(3) is 1.19×10-11 esu. The value is larger than other polymers reported. PSB is self-focusing material and has potential application in nonlinear optic field.     

Nonlinear Optical Properties of Porphyrin Derivatives with Electron‐donating or Electron‐withdrawing Substituents

To investigate photoelectric properties of meso‐extended porphyrin derivatives with electron‐donating or electron‐withdrawing substituents, a series of functionalized porphyrin materials have been designed and synthesized by Suzuki coupling reaction. The meso‐extended structures were fully characterized by ¹H NMR, IR spectroscopy and mass spectrometry. The photophysical properties of porphyrin derivatives were carefully examined by UV‐Visible and fluorescence spectra, and the solvatochromic effect was observed and discussed. In particular, Z‐scan technique was employed to characterize the third‐order nonlinear optical (NLO) properties of the products such as nonlinear absorption and refraction, the third‐order nonlinear refractive indexes (??⁽³⁾‐value) of these porphyrin derivatives achieved 3.9×10^?12 esu. In addition, the compounds could be self‐assembled into highly organized morphologies through phase‐exchange method. All the results indicated that the discotic materials have the potential for optoelectronic applications.