金属酞菁衍生物的合成及三阶非线性光学性能

合成了四硝基酞菁钴、四氨基酞菁钴以及二硝基二氨基酞菁钴等金属酞菁衍生物。根据IR、UV—Vis和元素分析．确定了它们的结构。使用四波混频技术测量了它们在DMF溶液中的三阶非线性光学系数Z^[3]值,发现金属离子和酞菁环上的取代基对酞菁化合物的三阶非线性光学性能都有较大的影响,本文初步讨论了这些因素对三阶非线性光学性质的影响机理。     

3种偶氮化合物的合成及三阶非线性光学性能

合成了3种1,3,4-噻二唑偶氮化合物,其中1种为新化合物,用IR、1H NMR和元素分析表征了其结构.采用飞秒激光,运用简并四波混频法,研究了化合物在非共振状态下的三阶非线性光学性能.它们的三阶非线性光学极化率X(3)为(3.84～3.95)×10-13esu,非线性折射率n2为(7.07～7.27)×10-12esu,分子二阶超极化率γ为(3.56～3.72)×1031esu,响应时间τ为101fs.探索了化合物的分子结构对三阶非线性光学性能的影响.引入离域能小的芳杂环,形成吸供构型,增大取代基的吸或供电子能力等有利于获得较大的三阶非线性光学性能.     

非线性光学活性分子的三阶非线性极化率

设计和合成了６种具有非线性光学活性的给体－受体型偶氮化合物,用Ｚ－扫描技术测定了这些非一光学活性分子的非线性折射率及三阶非线性极化率,并讨论了偶氮化合物的分子结构与三阶非线性极化率的关系。     

具有离子识别能力的新型有机光致变色材料

有机光致变色材料是在特定波长的光照射下,生成同分异构体,同时在另一波长光照射或加热的条件下,该异构体可发生逆反应并伴随着明显的光物理化学性能变化的有机材料。将超分子化学的分子识别和光致变色相结合,可以实现客体操控材料的光致变色性能。基于其特殊的光切换性质,人们已开发出多种多响应、多功能材料并将其广泛应用于分子开关、分子逻辑门、分子机器、化学传感、生物成像等诸多领域。其中,具有离子识别能力的光致变色化合物因其易操作和廉价而成为最理想的该类材料之一。该类化合物不仅光致变色性质可以被离子所调节,同时也可以作为特异检测离子的新型光控探针。着重介绍近几年具有离子识别能力的光致变色材料的研究进展。最后结合现阶段的研究情况,对其前景和应用进行了展望。     

金属有机非线性光学材料

本文介绍了非线性光学的简史，非线性光学材料的分类及应用，简述了金属有机非线性光学材料的原理，从分子工程和晶体工程的角度讨论了金属有机非线性光学材料的结构与性质的关系，综述了目前已研究的金属有机化合物和金属有机聚合物的二阶、三阶非线性光学材料，二阶非线性光学材料按目前所做的工作可以分成二大类：一类是含有芳香基或杂环的过渡金属羰基化合物；一类是含有二茂铁基和吸电子基的共轭体系化合物。三阶非线性光学材料的研究工作主要集中在酞菁类的金属配合物上，本文对金属有机化合物作为非线性光学材料的独特之处进行了总结，并对金属有机非线性光学材料的前景作了展望。     

有机低分子三阶非线性光学材料

根据分子结构特征对各类有机低分子三阶非线性光学材料结构与性能的关系作了评述。根据三阶非线性光学基本原理对有机材料三阶非线性光学效应的机理和材料的分子设计作了分析。     

不对称酞菁化合物的合成及研究进展

综述了近年来不对称酞菁化合物的合成进展及不对称酞菁在有机非线性光学、电荷转移、催化剂,分子整流器等领域的研究与应用。     

醌构稠杂环系有机三阶非线性光学材料的合成和性质研究

分子设计并合成了三大系列的醌构稠杂环化合物,由有机光波谱分析验证了各化合物的结构。用一维简并四波混频实验测定并计算了各化合物溶液的红外区,非共振三阶非线性光学极化率Ｘ（３）和分子三阶非线性光学超极化率γ。研究了分子结构对三晨线性光学性质的影响。     

3种具有D-π-A-π-D构型化合物的合成及三阶非线性光学性能

合成了3种新的D-π-A-π-D构型的2,6-双[(取代苯基)偶氮]蒽醌化合物,并用IR,1H NMR和元素分析表征了其结构.采用飞秒激光,运用简并四波混频(DFWM)法,研究了化合物的三阶非线性光学性能.它们的三阶非线性光学极化率χ(3)为(3.75～3.93)×10-13esu,非线性折射率n2为(6.90～7.24)×10-12esu,分子二阶超极化率γ为(3.52～3.84)×10-31esu,响应时间为94～108fs.分析了化合物的分子结构对三阶非线性光学性能的影响.     

新型2-芳基咪唑并菲咯啉Ni(Ⅱ)配合物的合成及光学非线性

设计合成了3个新的含2-芳基-1H-咪唑并[4,5-f][1,10]菲咯啉的Ni(Ⅱ)配合物,用UV、IR、MS和元素分析进行了表征。采用飞秒激光,运用简并四波混频法,研究了Ni(Ⅱ)配合物在非共振状态下的三阶非线性光学性能。它们的三阶非线性光学极化率χ(3)为(3.99～4.36)×10-13esu,非线性折射率n2为(7.33～8.03)×10-12esu,分子二阶超极化率γ为(3.98～4.37)×10-31esu,响应时间τ为50～86fs。探索了配合物的分子结构对三阶非线性光学性能的影响。结果表明扩展π电子共轭体系,增强非平面分子内电荷转移等因素有利于获得较大的三阶光学非线性。     

The effect of aggregation on the nonlinear optical absorption performance of indium and gallium phthalocyanines in a solution and co-polymer host

The nonlinear optical properties (NLO) of Pcs can be modified by substituting different metal atoms into the ring or altering peripheral and axial functionalities. In this study, nonlinear optical absorption properties of tetra-substituted gallium and indium phthalocyanine complexes both in solution and polymeric film have been investigated by open aperture Z-scan measurements with nanosecond pulses at 532 nm. All investigated compounds exhibited reverse saturable absorption for both solution and film experiments. The investigated compounds in the solution showed better nonlinear optical absorption properties than polymeric films. The observed nonlinear optical absorption differences depending on the aggregation are discussed using the ultrafast dynamics and decay processes of excited states found from femtosecond pump-probe spectroscopy with white light continuum experiments.     

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.     

回顾与展望:酞菁及其应用

本文介绍了酞菁化合物的简史;综述了酞菁化合物薄膜的制备方法。对酞菁化合物在光电导体,能量转换器,非线性光学,发光,气体传感器,变色和有机超晶格结构等方面的应用和存在的问题作了详细描述;并对酞菁化合物的应用前景作了展望     

Phthalocyanines

Progress in recent investigations of phthalocyanines (Pcs) and their analogues has been reviewed with emphasis on the work carried out in 1998. In particular, the synthesis and identification of low symmetrical Pc analogues or dendritic and optically active Pcs, and the characterization of Pcs by newly developed analytical and spectroscopic methods, are described.     

非线性光学晶体LiB_3O_5研究进展(英文)

综述了硼酸盐非线性光学晶体LiB3O5(LBO)的研究进展。首先介绍了硼酸盐非线性光学晶体的背景及现状,重点介绍了硼酸盐非线性光学晶体的典型代表——LBO晶体的相关研究内容。然后从LBO晶体作为非线性光学晶体材料的发现到晶体生长和它在全固态激光中的应用等方面进行了讨论。最后,介绍了研究组过去几年中在LBO晶体研究方面取得的成果并展望了LBO晶体研究的未来发展方向。     

Organic materials for nonlinear optics

This review discusses nonlinear optical (NLO) polymeric materials. As an example of a second-order NLO material, a novel copolymer with a diazo dye attached is investigated. The second-order NLO coefficient χ⁽²⁾ of the copolymer reaches 1.0 × 10^?6 esu, which is 7 times larger than that of LiNbO₃. A third-order NLO coefficient χ⁽³⁾ larger than 10^?10 esu is obtained for polymers where NLO dyes are introduced into the polymer backbone. The optical transmission loss of these polymers is revealed to be around 2 dB/cm. As these polymers can be formed into channel waveguides using the photo-bleaching technique, they show promise for use in NLO devices because of their processability, transparency and large optical nonlinearity.     

3R MoS2 with Broken Inversion Symmetry: A Promising Ultrathin Nonlinear Optical Device

Nonlinear 2D layered crystals provide ideal platforms for applications and fundamental studies in ultrathin nonlinear optical (NLO) devices. However, the NLO frequency conversion efficiency constrained by lattice symmetry is still limited by layer numbers of 2D crystals. In this work, 3R MoS₂ with broken inversion symmetry structure are grown and proved to be excellent NLO 2D crystals from monolayer (0.65 nm) toward bulk‐like (300 nm) dimension. Thickness and wavelength‐dependent second harmonic generation spectra offer the selection rules of appropriate working conditions. A model comprising of bulk nonlinear contribution and interface interaction is proposed to interpret the observed nonlinear behavior. Polarization enhancement with two petals along staggered stacking direction appears in 3R MoS₂ is first observed and the robust polarization of 3R MoS₂ crystal is caused by the retained broken inversion symmetry. The results provide a new arena for realizing ultrathin NLO devices for 2D layered materials.     

Novel photorefractive sol-gel materials

We have developed new photorefractive media based on hybrid organic-inorganic materials containing a charge transporting (CT) molecule either as side-chain or main-chain substituents on the silica backbone. Second order nonlinear optical (NLO) chromophores were introduced either as side chain or as guest units. These materials were prepared by the sol-gel process in the form of thin films of a few μm-thick. NLO and photorefractive properties have been evaluated using electro-optic measurements, two beam coupling experiments and photoconductivity measurements.     

Three-in-One Strategy Constructing the First High-Performance Nonlinear Optical Sulfide Crystallizing with the P43 Space Group

The balance between large nonlinear optical (NLO) effect and wide bandgap is the key scientific issue for the exploration of infrared NLO materials. Targeting this issue, two new pentanary chalcogenides KGaGe_1.37Sn_0.63S₆ ( 1 ) and KGaGe_1.37Sn_0.63Se₆ ( 2 ) are obtained by the three-in-one strategy, viz. three types of fourfold-coordinated metal elements co-occupying the same site. They crystallize in the tetragonal P4₃ ( 1 ) and monoclinic Cc ( 2 ) space group. Their structures can be evolved from benchmark AgGaS₂ (AGS) by suitable substitution. Remarkably, 1 is the first NLO sulfide crystallizing with the P4₃ space group, representing a new structure-type NLO material. The structural relationship between 1 and 2 and the evolution from 1 , 2 to AGS are also analyzed. Both 1 and 2 show balanced NLO properties. Specifically, 1 exhibits phase-matchable SHG response of 0.6 × AGS, a wide bandgap of 3.50 eV, and a high laser damage threshold of 6.24 × AGS. Theoretical calculation results suggest that the Ga/Ge/Sn element ratios of the co-occupied sites of 1 and 2 are the most appropriate for stabilizing the structures. The strategy adopted here will provide some inspiration for exploring new high-performance NLO materials.     

Fabrication of photonic nanostructures in nonlinear optical polymers

Two experimental techniques have been developed for creating photonic structures in nonlinear optical (NLO) polymers with precisions down to nanoscale. The first technique uses nanoimprinting technology to directly pattern the guest-host NLO polymers. It can be applied to the fabrication of photonic bandgap structures in NLO materials, as well as many other photonic structures in both linear and nonlinear polymers. The second technique utilizes self-assembly of NLO polymer monolayers onto a nanostructured template. This approach provides a highly effective means to implement practical waveguide devices using high performance self-assembled polymers with large electro-optic activity and inherent long-term stability. An optical switching device is proposed, based on nanofabricated NLO polymers.