Excited-state absorption of meso-tetrasulfonatophenyl porphyrin: Effects of pH and micelles

The influence of the environment on the excited state transitions of meso-tetrakis(p-sulfonatophenyl) porphyrin (TPPS) is reported. TPPS was investigated in protonated and non-protonated forms, and in the presence of the cationic cetyltrimethylammonium bromide (CTAB) micelles. The singlet excited-state absorption spectra were measured by using the white-light continuum Z-scan technique and the triplet–triplet absorption spectra were acquired employing an association of laser flash photolysis and Z-scan techniques. Our results show that the perseveration of the molecular symmetry, upon excitation, depends on the state of multiplicity of the molecules, as well as on the environment and structural characteristics of the porphyrin. Additionally, it was observed that for excited molecules, the ring distortion caused by the protonation of porphyrin ring has great influence on the changes observed for the symmetry and vibronic structure. The results clearly show that the porphyrin investigated is a promising candidate for optical limiting applications for all investigated environments.     

Nonlinear optical behavior of alkyne terminated phthalocyanines in solution and when embedded in polysulfone as thin films: Effects of aggregation

We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10⁻⁸ esu and ∼1.02 × 10⁻²⁶ esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.     

Nonlinear optical responses of erbium-doped YAG ceramics

By performing the Z-scan measurements with ultrafast femtosecond laser centered at 800 nm wavelength, we can unambiguously distinguish the real and imaginary part of the third-order optical nonlinearity of the erbium-doped YAG ceramics. The reverse saturable absorption of the erbium-doped YAG ceramics has been observed experimentally, and the nonlinear refractive index of the ceramics is estimated to be about 10⁻²¹ m²/W. The experimental results may provide design guidelines for the high power laser design and its applications.     

The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties

Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D_2d (Cu^I, Ag^I, Zn^II) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis[4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β_1.91 in the range of 211-340 × 10⁻³⁰ esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections.     

π电子共轭键结构对材料非线性光学性能影响研究

合成了具有不同π电子共轭键3个新的有机光学材料4-(吡啶-4-乙烯),4'-(N,N-二羟乙基氨基)二乙烯苯(a),N-((4-(N,N-二羟乙基氨基)-苯亚甲基)-4-(吡啶-4-乙烯)苯胺(b)和4-(吡啶-4-乙烯),4'-(N,N-二羟乙基氨基)偶氮苯(c),使用脉宽8ns波长532nm调Q倍频ns/ps Nd:YAG脉冲激光系统测试了它们的非线性光学性能,研究了分子结构与非线性光学性能之间的关系.结果显示这些化合物具有大的三阶非线性光学系数,这可能来源于它们长的D-π-A共轭电子结构;以N=N双键为共轭键的化合物的非线性光学性能优于以C=N或G=C双键为共轭键的化合物.     

双羟乙氨基-硝基型偶氮分子的三阶光学非线性

设计并合成了5种综合性能较好的双羟乙氨基给体-硝基受体型偶氮化合物,它们分别具有DπA型和DπAπD型共轭结构.用Z-扫描方法研究它们的三阶非线性光学性质.实验结果表明双羟乙氨基给体和硝基受体组合与偶氮共轭链相连组成的分子具有较大的三阶非线性极化率.其中化合物5具有DπAπD型共轭结构,它包含两条从N,N-双羟乙氨基给体到硝基受体的共轭链,因此较大的分子内电荷转移使三阶极化率γ达到2.958×10-33esu,并且在化合物的共轭链中引入具有较低离域能的芳香杂环能增大三阶极化率.     

Studies on nonlinear optical parameters of bis-chalcone derivatives doped polymer

Two bis-chalcone derivatives, 1,5-[di(4-methoxyphenyl)]penta-1,4-dien-3-one and 1,5-[di(4-chlorophenyl)]penta-1,4-dien-3-one were synthesized. Their SHG conversion efficiencies are reported to be 6.0 and 5.0 times that of urea and hyper polarizabilities are 9.9×10⁻³⁰ and 10.2×10⁻³⁰ esu, respectively. The third-order nonlinear optical properties in PMMA matrix were studied by Z-scan technique using 7 ns laser pulses at 532 nm. The nonlinear refractive index γ, nonlinear absorption coefficient β, magnitude of effective third order susceptibility χ⁽³⁾ and the coupling factor ρ have been investigated. The values obtained are of the order of 10⁻¹⁴ cm²/W, 1.2 cm/GW, 10⁻¹⁴ esu and 0.2, respectively, which are comparable with the values obtained in stilbazoleum like dyes. The experimental investigation also shows that they are very interesting optical limiting materials and their optical limiting behaviour is mainly due to two photon absorption phenomenon.     

Synthesis and Self-Organization of Fluorene-Conjugated Bisimidazolylporphyrin and Its Optical Properties

A conjugated-bisimidazolylporphyrin bridged by bis(ethynylfluorene) was synthesized and organized into linear polymer through self-coordination having mean molecular weights, M_w and M_n, of ~2.1 × 10⁵ Da and ~1.6 × 10⁵ Da, respectively. A large two-photon absorption cross section value of 3.4 × 10⁵ GM (per dimer unit) was observed. This value was comparable to that of the previously reported self-assembled linear polymer consisting of butadiyne-bridged imidazolylporphyrins. The two-photon absorption properties could be controlled by tuning the wavelength and absorption intensity of the one-photon absorption.     

Donor/acceptor effects on the nonlinear optical properties of 1,3 diphenyl propenones

Employing the single beam Z-scan technique with nanosecond laser pulses at 532 nm, the refractive and absorptive nonlinearities of donor and acceptor substituted (2E)-1-(3,4-dimethoxyphenyl)-3-phenylprop-2-en-1-one have been studied. The sign of the nonlinear index of refraction (n ₂) is found to be negative and the magnitude of n ₂ is in the order of 10^?11 esu. The second-order molecular hyperpolarizability (γ_h) is calculated to be in the order of 10^?32 esu. The variation of nonlinear absorption coefficient (β_eff) with input intensity (I ₀) is studied and the nonlinear absorption mechanism is found to be reverse saturable absorption (RSA). The enhancement of nonlinearity due to the donor and acceptor substitution is in accordance with the variation in π electron delocalization in the molecules. The compounds exhibit good optical limiting as well.     

AgOx型超分辨近场结构的非线性光学特性研究

采用共焦Z扫描系统，以λ=532nm．脉冲宽度0．7ns．重复频率15．79kHz的脉冲半导体激光器作为入射光源，研究了AgOx超分辨近场结构(SuperRENS)薄膜样品的非线性光学性质．实验获得了其三阶非线性折射率系数随入射光功率的变化曲线．并与Au，Ag薄膜作了比较．讨论了光致非线性变化过程。结果表明，在聚焦激光作用下．AgOx超分辨近场结构薄膜样品存在一相变点．即解析出纳米Ag颗粒，满足了产生局域表面等离子体的激发和增强效应的条件。