非对称双极性(D-π-A)吡啶Salophen席夫碱锌/镍配合物的合成、表征、线性及非线性光学性质研究

通过Still偶联反应合成了吡啶取代的香草醛(1a和1b)。以过渡金属离子(Zn²⁺和Ni²⁺)作为模板,以单亚胺席夫碱2和吡啶基香草醛为原料合成和表征了新的非对称双极性(D-π-A)Salophen金属配合物(3a、3b和3c)。测定了这些金属配合物的线性和三阶非线性光学(双光子吸收,TPA)性质。双极性的Salophen金属配合物的发射光谱在可见光范围内(486~516nm),荧光寿命4.51ns~5.18ns,荧光量子产率在4.3%~5.3%之间。衰减时间测试表明,荧光寿命是在纳秒级范围,这表明该发射来自单线态。对这些化合物进行了热重分析,结果表明3a、3b和3c都是热稳定的,起始分解温度(T_d)为333~374℃。使用开孔Z-扫描方法在800nm处用100fs脉冲的激光对这些双极性的Salophen金属配合物的TPA截面σ⁽²⁾进行了测试,最高可达1403GM,其值为目前已知席夫碱金属配合物较高值之一。测试表明,锌的Salophen金属配合物具有良好的荧光量子产率、巨大的TPA截面σ⁽²⁾、很高的热稳定性以及锌配合物公认的低毒性。因这些配合物可以被近红外或红外波长的光激发,这种光可以有效地穿透生物组织同时减轻细胞损伤,所以Salophen锌配合物作为双光子荧光发色团在生物体成像中有潜在的应用。     

Mesogenic ketohexose and aldopentose derivatives: anomalous behaviour of the alkyl D-fructopyranosides

The thermotropic and lyotropic behaviour of a number of alkyl ketopyranosides, alkyl ketofuranosides, an alkyl pentopyranoside and an alkyl pentofuranoside were studied. With the exception of the alkyl beta-D-fructopyranosides, all the compounds display the expected smectic A* phases. The three alkyl fructopyranoside homologues studied (octyl, decyl and dodecyl) display a novel, rather viscous mesophase (monotropic), the nature of which is as yet unclear. The unknown phase is not a smectic A phase, because a phase transition from smectic A* to phase X is observed for both the decyl and the dodecyl derivative. The lyotropic behaviour of all the compounds in this study is quite similar to that reported earlier for other monoalkylated monosaccharide derivatives, except that the unknown phase X is again observed for the fructopyranoside derivatives.     

Z-scan study of third-order optical nonlinearities in bismuth-based glasses

The third-order optical nonlinearity was measured in bismuth-based glasses by Z-scan technique using femto-second laser pulses. Re(χ⁽³⁾) = 4.9 × 10⁻¹¹ esu at 748 nm was obtained in the glass containing 65.5 mol% of Bi₂O₃. Although, the wavelength dependence of Re(χ⁽³⁾) shows resonant effect significantly, relatively small nonlinear absorption coefficient β = 0.8 cm/GW at 769 nm was estimated. Bismuth-based glass exhibits the largest third-order optical nonlinearity in oxide glasses, indicating they are promising materials used for nonlinear optical devices.     

飞秒激光惰性气体Ar原子多次电离过程的空间分辨研究

使用100飞秒、1014 W/cm2的强激光与惰性气体Ar原子相互作用,我们利用飞行时间质谱仪结合Z扫描技术获得了各次电离的Ar原子在激光焦点附近不同位置处强度分布.测量得到的各个不同电离态Ar n+(n=1～4)的产额随激光焦点位置变化关系与不同电离态的空间分布理论预言相一致.     

Photoswitching of the third-order nonlinear optical properties of azobenzene-containing phthalocyanines based on reversible host–guest interactions

Two water soluble azobenzene and phthalocyanine dyads with D–π–A alignment were synthesized. It was found that both compounds showed very large molecular cubic hyperpolarizabilities which are at the order of 10⁻³⁰ esu as the result of their unique chemical structure. The azobenzene moieties of these compounds, upon alternating illumination of UV and visible light, could reversibly associate with α-CD to form inclusion complexes through host–guest interaction in aqueous media, resulting in apparent influences to the 3rd NLO properties of these compounds. This influence is especially significant for the phthalocyanine whose central metal atom is copper (II). The molecular cubic hyperpolarizability γ of the inclusion complex for the copper phthalocyanine is 2.1 × 10⁻³⁰ esu. When the inclusion complex dissociated under the illumination of 365 nm light, γ value increased to 4.2 × 10⁻³⁰ esu, which is a 100% enhancement. Taking account of the large molecular cubic hyperpolarizabilities of these compounds, the present materials are potential as ideal 3rd NLO photoswitching systems.     

Wavelength dependent resonant nonlinearities in a standard saturable absorber IR26 on picosecond time scale

Nonlinear optical properties of a standard dye IR26 have been studied by using the Z-scan technique to decipher the difference in the mechanism of nonlinear absorption on picosecond time scale at two wavelengths i.e. at 1064 nm and 532 nm. A prominent contribution of nonlinear absorption is observed in the Z-scan profiles at 1064 nm. The dye exhibits the mechanism of self-defocusing at 1064 nm in contrast to that of self-focusing at 532 nm. While the two photon absorption has been found to be the dominant mechanism of reverse saturable absorption at 1064 nm, the mechanism of excited state absorption is operating at 532 nm. Additionally, the optical phase conjugate geometry of degenerate four wave mixing (DFWM) technique has been used to measure the third order nonlinear susceptibility values at 532 nm to compare with those obtained from the Z-scan profiles.     

Optical limiting properties of CdS nanowires

Intensity-dependent nonlinear optical transmission studies of cadmium sulfide (CdS) nanowires (∼ 50-100 nm diameter) suspended in dimethylformamide have been carried out in the visible region using the Z-scan technique with 7 ns pulses from the second harmonic of an Nd:YAG laser. The optical limiting threshold of CdS nanowires suspension was determined to be 1.3 J cm^− 2, with normalized transmittance of 0.47, which is relatively lower when compared with those of many popular metal nanowire suspensions reported in the literature. Based on an effective three-photon absorption model, nonlinear absorption and nonlinear scattering were identified as the dominant processes for the measured reduced transmittance.     

Optical limiting properties of zinc phthalocyanines in solution and solid PMMA composite films

The nonlinear absorption and optical limiting (OL) performance of tetra- and octasubstituted zinc phthalocyanine complexes were described in solution and in the solid state using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The polymeric films exhibit a much larger effective nonlinear absorption coefficient in comparison with solution. However, the parameters of the ratio of the excited to ground state absorption cross section and energy-dependent saturation in solution are much better compared to properties in the polymeric film. In terms of the ratio of the excited to ground state absorption cross section, the peripherally substituted complexes show better OL performance than the non-peripherally substituted derivative.     

Nonlinear optical responses of Sudan IV doped liquid crystal by z-scan and moiré deflectometry techniques

The nonlinear optical properties of a nematic liquid crystal doped with an azo dye were investigated. The magnitude and the sign of the third-order nonlinear refractive index, n₂, were measured using both single-beam z-scan and moiré deflectometry techniques. The measurements were performed at 532 nm using a Nd:Yag CW laser. The positive sign showed that sample which was studied possess a self-focusing optical nonlinearity. Rather close agreement was found between the values for n₂ obtained by z-scan and by moiré deflectometry. The nonlinear refractive index was found to be in the order of 10^− 6 (cm²/W) and the nonlinear absorption coefficient to be β = 0.171 (cm/W).     

可溶性多壁碳纳米管光限幅机理研究

根据光限幅与Z扫描实验研究了可溶性多壁碳纳米管的光限幅机理.通过现象分析、数据处理以及类比研究,证实材料的光限幅特征符合非线性吸收效应.对厚样品的独特现象进行了解释,讨论了其他机理的影响.根据Z扫描公式,计算了实验材料的三阶非线性系数.通过分析证实了非线性吸收在可溶性多壁碳纳米管的光限幅中发挥着主要作用.对厚介质的特殊现象进行的分析和计算表明,对于较厚介质和激光连续加热的情况下,其他机理的影响并不能完全否定,其特殊现象可能与微气泡的气穴作用有关.