有机二阶非线性光学发色团的研究进展

近年来,科学家们通过引进杂环片段、采用双(或多)官能化以及运用分子间弱相互作用等方法,在二阶非线性光学发色团的性能优化方面取得了较大进展.结合本课题组的研究,对此领域的研究进行了较全面的综述,并特别针对“非线性-透光性”矛盾的解决途径进行了较为详细的介绍.     

兼具大的二阶光学非线性与良好透明性的有机生色团的分子设计进展

从采用特殊的共轭桥、寻求给受体强度的最佳组合及设计双（多）重电荷转移 分子三方面，综述了近几年来在兼具较大分子一阶超极化率与良好透光范围的有机 二阶非性光学生色团的研究进展。     

含呋喃共轭桥有机非线性光学生色团的合成及性能研究

通过两次羟醛缩合反应合成了一种含呋喃共轭桥的有机非线性光学生色团分子2-二氰亚甲基-3-氰基-4-[2-(4-二乙氨基-苯乙烯基-呋喃基-5)-乙烯基]-5,5-二甲基-2,5-二氢呋喃(EFFC), 用IR谱、¹H NMR谱以及元素分析表征确认了其结构. 热失重分析表明, 材料的热分解温度T_d为250℃. 用密度泛函理论的B3LYP方法在6-31G基组下对这种生色团分子进行了结构优化, 并在相同基组下对分子的静态二阶极化率进行了计算, 分子的b₀=6.5×10^-28 esu. 将分子以18%的质量比与聚砜进行主-客体掺杂, 用溶胶凝胶法制备成膜后进行极化, 用二次谐波法对掺杂极化聚合物薄膜的电光系数进行测量, 其r₃₃值最高达到80 pm/V.     

Synthesis and Nonlinear Optical Properties of Chromophores with 1,8-Dimethoxy-9,10-dihydroanthracene and Ring-locked Triene

The new chromophore molecules with nonlinear optical （NLO） properties were prepared by Knoevenagel condensation from 1,8-dimethoxy-4,5-diformyl-9,10-dihydroanthracene and isophorone derivative in the presence of piperidine and acetic acid. In these chromophore, the ring-locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The key intermediate dialdehyde was conveniently prepared via a three step reaction, in which 1,8-dimethoxyanthraquinone was reduced with zinc/acetic acid and sodium/ethanol successively, followed by formylation with 1,1-dichlorodimethyl ether in the presence of TiCI4. The solvatochromism and UV spectra indicate that they have higher second-order nonlinear hyperpolarizability μβ values than the corresponding reference compound, without red shift of the charge transfer band.     

多烯和花菁染料分子设计及其非线性光学性质研究进展

根据一种新的增强分子非线性光学性质的设计思想 ,讨论了多烯和花菁染料的结构和性质关系 ,综述了这类染料的非线性光学性质及其应用进展 ,并对有机非线性光学材料的发展前景进行了预测。     

双光子吸收聚合引发剂EPVPVC的合成和非线性光学性质的研究

合成了一个新的双光子吸收聚合引发剂,9-乙基-3-{2-[4-(2-吡啶基-4-乙烯基)-苯基]-乙烯基}-9氢咔唑 (EPVPVC),用¹H NMR谱、¹³C NMR谱和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、单光子荧光寿命、单光子荧光量子产率和双光子荧光光谱.量化计算结果表明,EPVPVC的双光子吸收截面为56.6×10^-50 cm⁴·s·photon^-1.在780 nm的飞秒脉冲激光激发下,EPVPVC发出较强的上转换荧光,荧光峰位于536 nm.用EPVPVC做引发剂,加入丙烯酸酯型齐聚物(cN120C80),在脉冲宽度为200 fs,重复频率为76 MHz,中心波长为780 nm 飞秒脉冲激光下,制作了一个三维周期性微结构.在理论计算的基础上,定性地探讨了其可能的聚合机理.     

对位取代二苯乙烯衍生物的合成和非线性光学性质

合成了反式-4-[N-（乙氧基羰基-4"-硝基苯基）-N'-乙基氨基]-4'-(二甲基氨 基)二苯乙烯(DMANHAS)和三个新有机化合物。用核磁、红外以及元素分析进行了表 征。测试了紫外吸收光谱、单光子荧光光谱和双光子荧光光谱。在800nm的飞秒脉 冲激光激发下,反式-4-（N-羟乙基-N'-乙基氨基）-4'-(二甲基氨基)二苯乙烯 (DMAHAS)和反式-4-(N-羟乙基-N'-乙基氨基)-4'-(二乙基氨基)二苯乙烯(DEAHAS) 均发出较强的蓝紫色上转换荧光,荧光峰分别位于436和440nm,而DMANHAS和反式- 4-[N-(乙氧基羰基-4"-硝基苯基)-N'-乙基氨基]-4'-（二乙基氨基）二苯乙烯 (DEANHAS)没有荧光。     

芘基查尔酮的合成及三阶非线性光学性质

合成了一种新的具有潜在应用价值的非线性光学(NLO)有机材料1-(芘-1-基)-3-(4-二甲氨基苯基)丙烯酮(PMAK),并通过 NMR、IR、MS和元素分析等技术手段进行了表征。 采用溶液Nd:YAG激光技术测定了PMAK的三阶非线性光学性质并确定了相关参数。 纳秒实验结果:折射率n₂=-3.5×10^-17 m²/W,吸收系数β=7.0×10^-10 m/W,极化率χ⁽³⁾=2.54×10^-11 esu,分子超极化率γ=3.44×10^-30 esu;皮秒实验结果:n₂=-2.8×10^-18 m²/W,β=8.3×10^-11 m/W,χ⁽³⁾=2.49×10^-12 esu,γ=3.33×10^-31 esu。     

Convenient Synthesis and Enhanced Second-order Nonlinear Optical Property of a Novel Hyperbranched Polymer

A novel hyperbranched polymer （3） was prepared by copolymerization of tri-aldehyde moieties with azo chromophores having two active methelene groups, from ＂A2＋B3＂ approach based on simple Kneovenagel reaction. For comparison, its analogue linear polymer （5） was also synthesized. The two polymers are soluble in common organic solvents, and exhibit good thermal stability. Interestingly, the hyperbranched polymer demonstrates dramatically enhanced second-order nonlinear optical property with comparison to its linear analogue.     

若干有机非线性光学材料的分子设计及三阶非线性光学性质的理论研究

以ＩＮＤＯ／ＳＣＩ方法为基础,利用完全态求和（ＳＯＳ）公式,计算了若干有机非线性光学材料分子的三阶非线性光学系数γ（－ω; ω, －ω, ω）和γ（０; ０, ０, ０）,研究了γ与分子骨架、给电子取代基、噻吩环数目即：共轭分子链长的关系。设计了较大γ的新型非线性光学材料分子。     

新型光敏剂——系列尾式卟啉二肽的合成与光学性质研究

以5-(4-氨基苯基)-10,15,20-三苯基卟啉、叔丁氧羰基(Boc)保护的氨基酸为原料合成了系列新型尾式氨基酸卟啉和尾式卟啉二肽, 用核磁、质谱及元素分析对产物进行了表征, 并研究了其光学性质. 结果表明: 所合成的系列尾式卟啉二肽产率高达94%以上, 在可见光的红光部分有强烈的荧光发射.     

两个以杂环为共轭桥、含三苯胺基团化合物的合成及其发光性能

我们成功地合成了两种以杂环为共轭桥、含三苯胺基团的“D-π-D”型小分子, 初步研究结果表明：它们可以作为有机发光材料得到实际的应用。     

Synthesis and Characterization of a Series of New Functional Poly(ferrocenylenesilanes) for Nonlinear Optics

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含2，2′-联吡啶配体簇合物的合成、晶体结构及非线性光学性质

The Cluster compound [Cu₃BrWOS₃(bipy)₂] was synthesized by reaction of (NH₄)₂WOS₃， CuBr， 2，2′- bipyridine and n-Bu₄NBr at room temperature and characterized by IR， UV and elemental analyses. The structure of [Cu₃BrWOS₃(bipy)₂] was determined by single crystal X-ray diffraction revealing that the cluster consist of a nest -shaped core. The W atom is tetrahedrally coordinated by three S atoms and one O atom. There are two types of copper atoms in the WOS₃Cu₃ aggregate： two copper atoms are tetrahedrally coordinated and another copper atom is trigonally coordinated. The nonlinear optical properties were studied with an 8ns pulsed laser at 532nm. Its optical responses to the incident light exhibit considerably optical absorptive and strong self-focusing effect with α₂=0.90×10^-10m·W^-1， n₂=2.72×10^-18m²·W^-1. CCDC： 196348.     

1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮的合成及三阶非线性光学性质

合成了一种新的有机非线性光学(NLO)材料1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮(PMPAK),通过¹H NMR、IR、HR-MS和元素分析表征其结构。 以Nd:YAG-Laser System作为光源,激光波长450 nm,脉冲宽度4 ns(FWHM),采用4f相位相干成像技术测定了PMPAK的三阶NLO性质并确定了相关参数:非线性折射率n₂=-1.84×10^-16 m²/W,非线性吸收系数β=2.53×10^-9 m/W,非线性极化率χ⁽³⁾=1.137×10^-10 esu。     

K_2W_3SeO_(12)的合成、晶体结构和非线性光学性质研究

本文通过水热反应得到一种新化合物K2W3SeO12,并测试了其单晶结构,该晶体属于三方晶系,空间群R3c,晶胞参数a=b=c=1.253 61(10)nm,α=β=γ=33.539 0(10)°。对它进行了XRD、EDX、ATR-FTIR、UV-Vis-NIR、TG、SHG测试。测试结果表明化合物有很强的可实现相位匹配的粉末倍频效应(强度约为KDP的9倍),而且具有较宽的带隙(3.24 eV)和良好的热稳定性。粉末的红外吸收边达到10μm。结果表明K2W3SeO12是一个具有潜在应用价值的中红外非线性光学晶体材料。     

K2W3SeO12的合成、晶体结构和非线性光学性质研究

本文通过水热反应得到一种新化合物K₂W₃SeO₁₂,并测试了其单晶结构,该晶体属于三方晶系,空间群R3c,晶胞参数a=b=c=1.25361(10)nm,α=β=γ=33.5390(10)°。对它进行了XRD、EDX、ATR-FTIR、UV-Vis-NIR、TG、SHG测试。测试结果表明化合物有很强的可实现相位匹配的倍频效应(强度约为KDP的9倍),而且具有较宽的带隙(3.24eV)和良好的热稳定性。粉末的红外吸收边达到10μm。结果表明K₂W₃SeO₁₂是一个具有潜在应用价值的中红外非线性光学晶体材料。     

Mild Hydrothermal Synthesis and Optical Properties of the Complex Fluoride KMgF_3 Doped with Eu

Perovskite complex fluorides have attracted great interests due to their particular physical properties such as antiferromagnetic characteristics1, photoluminescence behavior2. Complex fluorides are usually prepared by solid state reactions at high-temperature. In spite of inert atmosphere, it is inevitable to contain a bit of oxygen. This has great effect on the luminescent character of rare earth ions. There are also reports about synthesizing some binary fluorides by high-temperature hy…