摘要
有机非线性光学材料尤其是有机三阶非线性光学材料是当前有机功能材料的前沿研究课题之一。有机三阶非线性光学材料可广泛应用于光通信、光计算、光存储、光全息术、激光医疗和激光武器等领域。
论文设计并合成了双偶氮-9，10-蒽二酮，偶氮-1，3，4-噻二唑，对称型苯并二呋喃酮等三大系列共41个可用作有机三阶非线性光学材料的新型有机色素类化合物；研究了化合物在非共振状态下的三阶非线性光学性能；探讨了分子结构与三阶非线性光学性能之间的关系。
以2，6-二氨基蒽醌或1，5-二氨基蒽醌为原料，用亚硝酰硫酸进行双重氮化，再与苯胺、苯酚或取代苯酚发生偶合反应合成了16个双偶氮-9，10-蒽二酮类化合物，其中14个为新化合物，收率为14.0～65.2％。
以甲酸或乙酸为原料，与氨基硫脲脱水环合制备了2-氨基-1，3，4-噻二唑和2-氨基-5-甲基-1，3，4-噻二唑，收率分别为63.4％和64.3％。以对氯苯甲醛为原料，与氨基硫脲先缩合，再用三氯化铁氧化环合制备了2-氨基-5-对氯苯基-1，3，4-噻二唑，收率为47.3％。制得的2-氨基-5-烃基-1，3，4-噻二唑用亚硝酰硫酸进行重氮化，再与苯酚、取代苯酚或萘酚发生偶合反应合成了21个偶氮-1，3，4-噻二唑类化合物，其中16个为新化合物，收率为19.6～58.8％。
以苯甲醛或取代苯甲醛为原料，与氯仿和氢氧化钠用相转移催化法制备了扁桃酸或取代扁桃酸，收率为86.8～90.1％。制得的扁桃酸或取代扁桃酸与对苯二酚脱水环合，再经氧气氧化合成了4个对称型苯并二呋喃酮类化合物，其中1个为新化合物，收率为32.6～40.0％。
41个目标化合物由IR、~1H NMR和元素分析进行了结构确证和UV吸收光谱性能测定。探索了化合物的合成方法和反应机理过程，实验考察了关键合成反应的工艺条件。
在分析三阶非线性光学性能原理和参数模型的基础上，采用飞秒激光，应用简并四波混频测量技术，测试并计算拟合了41个目标化合物在非共振状态下的三阶非线性光学极化率χ~(3)，非线性折射率n_2，分子二阶超极化率γ，以及响应时间τ等性能参数。双偶氮-9，10-蒽二酮类化合物的χ~(3)为2.62～3.93×10~(-13)esu，n_2为4.82～7.24×10~(-12)esu，γ为2.57～3.84×10~(-31)esu，τ为86～116fs。偶氮-1，3，4-噻二唑类化合物的χ~(3)为3.31～4.29×10~(-13)esu，n_2为6.08～7.89×10~(-12)esu，γ为3.44～4.29×10~(-31)esu，τ为69～112fs。对称型苯并二呋喃酮类化合物的χ~(3)为2.86～3.21×10~(-13)esu，n_2为5.26～5.91×10~(-12)esu，γ为2.92～3.42×10~(-31)esu，τ为88～98fs。
探索了分子结构与三阶非线性光学性能之间的关系。离域能小的共轭骨架，非中心对称结构，长的共轭链，吸供取代基的引入，取代基强的供电子性或吸电子性，长的吸供电子取代基之间的距离，以及良好的共平面程度等因素有利于获得较大的三阶非线性光学性能。
In the rapidly growing field of the organic functional materials,organic nonlinear optical (NLO) materials, especially of the third-order, areat the forefront of research activities. Organic third-order nonlinear opticalmaterials have numerous applications, such as optical fiber communication,optical computing, optical data storage, dynamic holography, laser medicaltreatment, laser weapon and so on.
Three series of 41 novel organic chromophore compounds such asbisazo-9,10-anthracenedione, azo-1, 3, 4-thiadiazole and symmetricalbenzodifuranone were designed and synthesized in the dissertation. Theoff-resonant third-order optical nonlinearities of these novel compoundswere investigated.The influence of the molecular structures on thethird-order optical nonlinearities was studied.
A series of 16 bisazo-9,10-anthracenedione compounds weresynthesized by bisdiazotizing of 2,6-diaminoanthraquinone or 1,5-diaminoanthraquinone with nitrosylsulfuric acid, then coupling withaniline, phenol or substituted phenol. The yields were 14.0～65.2%. 14 ofthem were new compounds.
2-Amino-1,3,4-thiadiazole and 2-amino-5-methyl-1,3,4-thiadiazolewere prepared by dehydrating cyclization of formic acid or acetic acid withthiosemicarbazide. The yields were 63.4% and 64.3%, respectively.2-amino-5-(p-chlorophenyl)-1,3,4-thiadiazole were prepared bycondensation of p-chlorobenzaldehyde with thiosemicarbazide, thenoxidative cyclization with ferric chloride. The yield was 47.3%. A series of21 azo-1,3,4-thiadiazole compounds were synthesized by diazotizing of2-amino-5-alkyl-1,3,4-thiadiazole with nitrosylsulfuric acid, then couplingwith phenol, substituted phenol or naphthol. The yields were 19.6～58.8%.16 of them were new compounds.
Mandelic acid or substituted mandelic acid were prepared by phasetransfer catalysis of benzaldehyde or substituted benzaldehyde withchloroform and sodium hydroxide. The yields were 86.8～90.1%. A seriesof 4 symmetrical benzodifuranone compounds were synthesized bydehydrating cyclization of mandelic acid or substituted mandelic acidwith hydroquinone, then oxidation with oxygen. The yields were 32.640.0%. 1 of them was the new compound.
The structures of 41 desired compounds were confirmed by UV, IR,~1H NMR and elemental analysis. The synthetic methods and mechanisms of reaction were studied. The process parameters were evaluatedexperimentally.
By using femtosecond laser, the third-order optical nonlinearities of41 desired compounds were measured with the geometry of DegenerateFour-wave Mixing (DFWM) technique. The third-order nonlinear opticalsusceptibilities x~(3), the nonlinear refractive indexes n_2, the second-orderhyperpolarizabilities of the moleculesγand the response timesτwerecalculated based on the principle of the third-order optical nonlinearity. Asfor bisazo-9,10-anthracenedione compounds, the x~(3) were 2.623.93×10~(-13)esu. The n_2 were 4.82～7.24×10~(-12)esu. Theγwere 2.573.84×10~(-31)esu. Theτwere 86～116 fs. As for azo-1, 3, 4-thiadiazolecompounds, the x~(3) were 3.31～4.29×10~(-13)esu. The n_2 were 6.087.89×10~(-12)esu. Theγwere 3.44～4.29×10~(-31)esu. Theτwere 69～112 fs.As for symmetrical benzodifuranone compounds, the x~(3) were 2.86～3.21×10~(-13)esu. The n_2 were 5.26～5.91×10~(-12)esu. Theγwere 2.923.42×10~(-31)esu. Theτwere 88～98 fs.
The influence of the molecular structures on the third-order opticalnonlinearities was studied. The factors such as conjugate framework withsmall conjugation energy, central asymmetry, long conjugate chain,introduction of electron donors-acceptors, strong electron-donating orelectron-withdrawing abilities, long distance between electron donors andelectron acceptors, good coplanarity and so on lead to high third-order optical nonlinearities.
引文
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