稀土酞菁配合物的研究进展

１前言酞菁配合物是一类热稳定性和化学稳定性都很高的化合物,具有优良的耐酸、耐热、耐晒、色泽鲜艳等性能,并且对一些较强的氧化还原性试剂有很好的抑制作用,因此广泛用于颜料、染料、印染工业。酞菁还被用作光导、光电、二维有机导体和三阶非线性光学研究的材料。稀...     

荧光酞菁复合凝胶玻璃的光限幅行为及机理研究

Sol—gel法将两种具有较高荧光量子产率的四磺化酞菁锌（ZnTSPc）、酞菁氯镓（GaPcCl）分别植入二氧化硅凝胶基质，制备均匀掺杂的复合凝胶玻璃，并对其荧光效应和光限幅性能进行测试。从荧光发射的角度佐证了无机基金属酞菁复合材料的光限幅效应是基于酞菁分子的反饱和吸收机理。     

卟啉衍生物在光限幅中的应用

介绍了卟啉作为光限幅材料的研究现状,同时综述了卟啉光限幅材料的分子设计、结构与性能的关系,并展望了其应用前景。     

氯铝酞菁复合凝胶玻璃的制备及光限幅效应研究

采用溶胶-凝胶(Sol-gel)工艺在二氧化硅(SiO2)凝胶玻璃基质中掺入氯铝酞菁(AlPcCl),制备了掺杂AlPcCl的复合凝胶玻璃;采用透射电子显微镜、扫描电子显微镜研究了AlPcCl复合凝胶玻璃的组成和结构,并且分析了掺杂浓度对其紫外-可见吸收光谱的影响;通过开孔Z-扫描测试和激发态吸收谱测试对复合干凝胶的光限幅效应和机理进行了探索.结果表明均匀掺杂AlPcCl的复合凝胶玻璃具有优于AlPcCl在DMF溶液中的光限幅效应,其主要机理为非线性散射,这为新型复合光限幅材料的制备提供了理论基础.     

酞菁分子结构特征对复合凝胶玻璃体系光限幅性能的影响

用溶胶凝胶法将2组具有不同分子结构特征的酞菁配合物分别植入二氧化硅凝胶基质,制备均匀掺杂的复合凝胶玻璃,并对其光限幅性能进行测试。研究结果表明:掺杂酞菁分子结构特征对其复合体系的光限幅性能有显著影响。掺杂无金属酞菁(phthalocyanine, H2Pc)和不同金属酞菁配合物(metallophthalocyanine, MPc)的硅氧凝胶玻璃,其光限幅效应随中心离子不同而异,并依 H相似文献   

酞菁配合物的合成、分离与表征

文章在溶液中温和的条件下合成了四硝基酞菁钴和四氨基酞菁钴配合物,该方法具有反应温度低、毒性小、产率高等特点,两种产物产率分别为60.0%和89.6%。并探索出柱层析法分离提纯四硝基酞菁钴的方法。通过紫外可见分光光度计和核磁共振仪对产物进行了表征。     

酞菁在光动力学疗法中的应用

本文着重从物理和光化学的角度讨论了酞菁在光动力学疗法中的作用原理、结构与性能的关系。     

溴代酞菁铁配合物的光谱电化学性质研究

本文对μ-氧-四溴酞菁铁配合物([TBPcFe]_2O)的电化学性质及光谱电化学性质进行了研究。结果表明,μ-氧-四溴酞菁铁在所研究的电压区问内经历了三个单电子氧化还原反应,其半波电势为0.06V,—0.75V及—1.33V(相对于甘汞电极),分别对应于Fe~(3+)/Fe~(3=)、Fe~(2+)/Fe~+及TBPc~(2-)/TBPc~(3-)电对的氧化还原反应。光谱电化学性质研究亦观察到相应酞菁配合物的特征光谱。     

酞菁铕镨钕配合物的合成及表征

研究了铕酞菁、钕酞菁和镨酞菁配合物的合成、提纯与表征的方法。合成及表征结果表明，合成所得酞菁化合物通过元素分析可知，具有纯度高、红外光谱表征推测结构可靠。紫外分析表明铕酞菁、钕酞菁和镨酞菁配合物特征吸收峰有相似之处。     

碳纳米管的光学性质及其在光限幅中的应用

碳纳米管是一种新型的碳材料,具有特殊的结构,独特的力学、电磁学和光学性质,已引起人们的极大兴趣。综述了近年来碳纳米管光学性质的研究进展及其在光限幅中的应用,并对今后的研究方向作了展望。     

Transparent niobate glass-ceramics for optical limiting

The construction of nonlinear optical materials featuring asymmetric transmission of light is of great technological importance for various applications, including optical switching and optical power limiting. A significant challenge is the scalable fabrication of material candidates with good photochemical stability, high optical transmittance, and excellent optical limiting performance. Here, we present a nanocrystallization avenue for constructing hybrid optical limiting materials that exhibit ultrafast and robust optical limiting performance. The experimental results show that the controllable relaxation of a niobate glass may lead to the clustering of Nb-O units and contracting of the bandgap. It results in the notable improvement in nonlinear optical properties, including the enhanced saturation irradiance (380 GW/cm²), doubly increased nonlinear coefficient, and decreased limiting threshold (200 GW/cm²). Our results suggest a promising material that exhibits promising applications for protecting eyes and sensitive components from laser-induced damage.     

酞菁衍生物的组装改性技术及应用研究进展

酞菁及金属酞菁的改性组装可以调变其结构和特性,进而开发出多种先进的功能材料。酞菁改性的理化方法包括聚合、取代、负载等手段,技术工艺包括气相沉积法、真空镀膜法、旋涂法、电化学聚合法、相转移法、溶胶-凝胶法、LB膜技术等。除用于染料和颜料外,酞菁衍生物的应用领域主要有新型功能材料(光敏材料、气敏材料等),新型仿酶催化剂(新型脱硫催化剂、有机反应的催化剂、新型水质处理剂等)。     

芴酮-芳香醛-双腙的合成、晶体结构及光限幅性能

合成了4种新的标题化合物,通过红外光谱、核磁共振、质谱及元素分析对它们结构进行了表征,并通过单晶X射线衍射确定了芴酮-N,N-二甲基苯甲醛-双腙的结构,结果表明该晶体为正交晶系,属Pbca空间群,具有较大的共轭体系和良好的平面性.采用Z-扫描技术测试了4种化合物的光限幅性能,研究表明其中3种化合物对532 nm激光有良好的光限幅性能,其双光子吸收截面分别为3.19×10-46、3.96×10-46和4.31×10-46 cm4*s/photon.     

Thermoset polymers as host for optical limiting

The human eye, sensors, and photoreceptors can be damaged if they are submitted to laser beams with high intensities and low divergence. In the military field, an optical sensor can be damaged by pulsed laser radiations when exposed beyond its capacities. In order to have a protection against such threats, passive optical limiting is used. A mix between a reactive oligomer and a monomer, with methacrylate functions, is studied in the present work giving a thermoset matrix. To prevent the monomer evaporation, which results in the formation of bubbles in the final material, related to the reaction exotherm, an oligomer and a monomer with a high boiling temperature are used as precursors, giving a good alternative to a thermoplastic matrix like polymethyl methacrylate (PMMA). We report the experimental results of transient thermally induced optical nonlinearities (i.e., nonlinear refraction) in methacrylate-based polymer filters at a nanosecond timescale, focus will be made to compare third order nonlinear refractive index from thermally induced refractive index. Optical filters are obtained by chemical bulk processes. In the present work, both thermoplastics and thermosets matrices were synthesized in order to characterize their optical limiting properties by mean of an appropriate custom-made optical setup as well as their nonlinear refractive indices measured by the z-scan technique. Optical measurements in the nonlinear regime are achieved at the wavelength of 1064 nm. To the best of the authors’ knowledge, such a work dealing on 3D-network methacrylate-based host has never been published.     

Laser protection with optical limiting by combination of polymers with dyes

Lasers are becoming more and more common and can damage eyes and sensors, so arise the need for efficient protection. A possibility is the use of filters with optical limiting abilities. Optical limiting leads to a reduced transmittance of these filters above a certain light energy. Solid-state optical limiting filters consist frequently of poly(methyl methacrylate) (PMMA). Using dyes is an often used way to provide optical limiting qualities to polymers. PMMA does not offer the possibility to attach the dye covalently to the polymer chain. Poly(lactide), also a transparent polymer, has so far not been used for filters for optical limiting. Its polymerization mechanism offers a simple possibility to a covalent binding of the dyes, by using them as initiator. This should be, like the attaching of big side groups to dyes, a possibility to increase stability of dyes against aggregation. Hybrids out of polymers and dyes and filters thereof could be produced. The polymers were analyzed by nuclear magnetic resonance, gel permeation chromatography, and nonlinear optical measurements. Including azophloxine leads to an attenuation of the laser beam in the range of 10⁻³ and Eosin B even to 10⁻⁵. The eosin sample shows a two magnitudes better attenuation then usual guest–host systems like poly(methyl acrylate) with carbon nanotubes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47150.     

Soluble functional polyacetylenes for optical limiting: Relationship between optical limiting properties and molecular structure

Four polyacetylenes containing chromophores with different conjugation bridge structure or terminal substituents were designed and prepared by using [Rh(nbd)Cl]₂ as catalysts, respectively. Their structures and properties were characterized and evaluated by IR, NMR, UV, TGA, optical limiting and nonlinear optical analyses. All the polymers show high thermal and photo stability and novel optical limiting properties. The functional polyacetylene with stilbene pendant shows better optical limiting property than that with azobenzene chromophore pendant. Their optical limiting mechanisms are mainly originated from reverse saturable absorption of molecules. Their nonlinear optical properties are significantly affected by their molecular structures and the shorter spacer group will be beneficial in increasing the electronic interaction between chromophore pendant and polyacetylene conjugation backbone to result in higher third-order optical nonlinearity.     

A promising optical limiting material: Tunable third-order nonlinear optical properties of robust CsPbX3 (X=Cl/Br,Br) nanocrystals glasses

As laser technology advances, the importance of laser protection puts an urgent demand for robust and high-efficient optical limiting materials. In this work, CsPbX₃ (X = Cl/Br, Br) NCs were synthesized by precisely controlling the ratio of Cl⁻ to Br⁻ and the heat treatment temperature, and the third-order nonlinear (TONL) optical properties of them were investigated systematically and deeply based on a nonlinear optical imaging technique with the phase-object (NIT-PO) at 532 nm for the first time. All of them demonstrate strong reverse saturation absorption (∼10^-12–10^-11 m/W), and the sign of TONL refraction index (γ) relates to the component (CsPb(Cl/Br)₃ NCs glasses: ∼10^-20 m²/W, CsPbBr₃ NCs glasses: ∼−10^-20 to 10^-19 m²/W). In addition, they have excellent characteristics of thermal stability and water stability, as well as photostability under 455 nm laser irradiation, indicating that it is a promising optical limiting material.     

Synthesis and properties of aluminum phthalocyanine side-chain polyimide for third-order nonlinear optics

A new third-order nonlinear optical polyimide with aluminum phthalocyanine unit as a side-chain (APSPI) has been developed. The poly(hydroxyimide) (PHI) was prepared by the ring-opening polyaddition of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride with 4,4′-diamino-4″-hydroxytriphenylmethane, followed by thermal imidization. The resulting PHI had number- and weight-average molecular weights (M_n, M_w) of 34,000 and 64,000, respectively. The introduction of aluminum phthalocyanine unit (AlPc) to PHI was carried out by the reaction of PHI with chloroaluminum phthalocyanine in the presence of silver triflate. The third-order nonlinear susceptibility χ(3) of APSPI film with approximately 60 mol% content of AlPc at 1064 nm wavelength was 5.3×10⁻⁹ esu. This was measured using the closed Z-scan technique.     

Incorporation of lead phthalocyanine into periodic nanolayered assemblies for advanced optical systems

Periodically structured polymeric materials can lead to the next generation of electro‐optic and nonlinear optical devices for applications in information technology. Layer‐multiplying melt coextrusion is an attractive method for fabricating periodic structures with thousands of alternating polymer microlayers or nanolayers. Many advanced applications for periodic polymeric structures would be enabled by locating a photoactive dye in one or both layers. However, it is anticipated that due to the thinness of the individual layers and the relatively low molecular weight of many dyes, a substantial fraction of the dye will diffuse from the doped layers into the undoped layers during melt coextrusion. In the present study, we demonstrate two methods for confining the activity of a photoactive dye, lead phthalocyanine, to the doped layers. Polycarbonate containing lead phthalocyanine was coextruded with undoped polyester as an assembly of 128 alternating 86 nm‐thick layers. Using the absorption spectra, we demonstrated that a high concentration of the monomer form persisted in the polycarbonate layers, whereas the lead form was converted to the less active lead‐free form in the polyester layers. Thus, the active monomer form of PbPc(β‐CP)₄ was maintained selectively in the polycarbonate layers. In the second approach, the coextrusion process was altered so that the alternating polycarbonate and polyester layers were separated by a thin layer of a barrier polymer. The barrier layer prevented diffusion of the dye during melt coextrusion and the dye remained selectively in the polycarbonate layers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fabrication of deodorizing fabric by grafting of metal phthalocyanine derivative onto nonwoven polypropylene fabric

Fabrication of deodorizing fabric was tried by grafting metal phthalocyanine derivative, a catalytic deodorant, onto polypropylene (PP) nonwoven fabric. Fe(III)-4,4′,4″,4‴-tetra carboxamide phthalocyanine (Fe-TCMP) was synthesized. The Fe-TCMP showed high-deodorizing performance when tested for the elimination of 2-mercaptoethanol, an index material for bad-smelling compounds. The Fe-TCMP was converted to Fe(III)-4,4′,4″,4‴-tetracarboxylic acid phthalocyanine (Fe-TCAP) by hydrolysis to have carboxyl groups. It was chemically grafted on the surface of PP nonwoven fabric, which was surface modified to have amine groups with diaminocyclohexane (DACH) plasma. Such fabricated deodorizing fabric showed high-deodorizing performance for 2-mercaptoethanol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 839–846, 2001