含芳茂铁基团三苯乙烯化合物的合成及光性能的研究
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摘要
本论文以芳酮和4-羟基二苯甲酮为原料，通过McMurry偶联反应合成了五种含有酚羟基的三苯乙烯化合物，分别为：1-苯基-2-(4-甲基苯基)-1-(4-羟基苯基)丁烯(TPE-1)、1,2-二苯基-1-(4-羟基苯基)丁烯(TPE-2)、1-苯基-1-(4-羟基苯基)-2-(4-氯苯基)丁烯(TPE-3)、1-苯基-1-(4-羟基苯基)-2-(4-苯氧基苯基)丁烯(TPE-4)、1-苯基-1-(4-羟基苯基)-2-(4-苯硫基苯基)丁烯(TPE-5)，在五种烯烃中，TPE-4和TPE-5未见报道。
以所合成的含有羟基的三苯乙烯化合物为原料，通过与氯苯芳茂铁盐的亲核取代反应，合成了五种含芳茂铁基团的三苯乙烯化合物，分别为：(η~5-环戊二烯)[η~6-1-(1-苯基-2-甲基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-1)、(η~5-环戊二烯)[η~6-1-(1，2-二苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-2)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-氯苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-3)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-苯氧基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-4)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-苯硫基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-5)，该五种茂铁盐均未见文献报道。
所制备的含羟基的三苯乙烯化合物和含芳茂铁基团的三苯乙烯化合物均经过IR、LC-MS、~1H-NMR和~(13)C-NMR进行表征，确定了物质结构。
对所合成的两类烯烃通过紫外可见吸收光谱研究发现,含芳茂铁基团的三苯乙烯化合物与含羟基的三苯乙烯化合物在200-350nm具有较强的吸收，取代基影响较小。引入茂铁盐后，在400-500nm产生由d-d跃迁产生的弱吸收。考查了溶剂极性对所合成的两类烯烃的紫外吸收光谱的影响，发现吸收峰随着极性的增大，峰型变窄，峰位红移。系统考查了所制备的两种烯烃在可见光下的光稳定性，含有羟基的三苯乙烯化合物具有很好的光稳定性，含有芳茂铁基团的三苯乙烯化合物随着光照时间的增长会有一定的光解。考查了所制备的两类三苯乙烯化合物的荧光发射光谱，研究发现在三苯乙烯化合物中引入芳茂铁基团，使三苯乙烯化合物的荧光减弱，荧光量子效率降低。
所制备的含芳茂铁基团的三苯乙烯化合物和含羟基的三苯乙烯化合物经热重研究发现，在240℃以下具有良好的热稳定性。此外发现引入芳茂铁基团后，TPE-Fc化合物比TPE化合物的热稳定性提高了60℃左右。
通过密度泛函理论(DTF)在B3LYP/6-31G**水平上，对所合成的三苯乙烯化合物进行了分子结构优化，发现三苯乙烯化合物在结构上不是平面型化合物，苯环和苯环之间具有一定的二面角；通过计算获得了前线轨道的能级及其电荷分布，发现同羟基三苯乙烯化合物相比，带有茂铁基的三苯乙烯化合物的HOMO轨道和LUMO轨道的能级差变小，并从HOMO轨道到LUMO轨道有明显的电荷转移；通过最优结构偶极距参数，计算了分子的一阶超极化率，发现在三苯乙烯化合物中引入茂铁基使分子的一阶超级化率显著提高。
Aryl ketone and4-hydroxyl dibenzophenone as raw materials, fivehydroxyl substituted triphenyl butene compounds were synthesized by theMcMurry coupling reaction, including1-(4-hydroxyphenyl)-2-(4-methylphenyl)-1-phenylbutylene(TPE-1),1,2-diphenyl-1-(4-hydroxyphenyl)butylene (TPE-2),2-(4-chlorophenyl)-1-(4-hydroxyphenyl)-1-phenylbutylenes(TPE-3),1-(4-hydroxyphenyl)-1-phenyl-2-(4-phenyloxyphenyl)but-ylenes(TPE-4),1-(4-hydroxyphenyl)-1-phenyl-2-(4-thiophenolphenyl)butyl-enes(TPE-5). Among the five hydroxyl substituted triphenyl butenecompounds, TPE-4and TPE-5were not reported.
Five triphenyl butane derivatives containing a cyclopentadienyl iron unitwere synthesized vis the SNAr reaction, including(η~5-Cyclopentadienyl)(η~6-1-(2-(4-methylphenyl)-1-phenyl)butyleneoxylphenyl] Fe hexafluorophosphate(TPE-Fc-1),[(η~5-Cyclopentadienyl)-Fe-(η~6-1-(1,2-diphenyl)butyleneoxylphenyl] Fe hexafluorophosphate(PHB-Fc-2),(η~5-Cycl-opentadienyl)(η~6-1-(2-(4-chlorophenyl)-1-phenyl)butyleneoxylphenyl] Fe he-xafluorophosphate(TPE-Fc-3),(η~5-Cyclopentadienyl)(η~6-1-(2-(4-phenylxyph- enyl)-1-phenyl)butyleneoxylphenyl] Fe hexafluorophosphate(TPE-Fc-4),(η~5-Cyclopentadienyl)(η~6-1-(2-(4-phenolthiophenyl)-1-phenyl) butyleneoxylphenyl] Fe hexafluorophosphate (TPE-Fc-5), all the compounds were not reportedbefore.
The structure of the target compounds were identified by IR, LC-MC,~1H-NMR and~(13)C-NMR.
The UV-Vis absorption properties of the target compounds were studied.TPE-Fc and TPE all show stronger absorption in200-350nm, and TPE-Fccompounds possesses weak absorption between400and500nm owing to thed-d transition of the cyclopentadienyl iron unit. The difference of substitutedgroup in TPE-Fc and TPE has little effect on the UV-Vis absorption. UV-Visabsorption of TPE-Fcs in various solvents with different polarities wereinvestigated and found that all showed positive solvatochromism(bathochromic shift) upon the increase in solvent polarity. The study ofphotolysis found that TPE is photostable, but TPE-Fc can carry out photolysis.From the fluorescence spectra of the target compounds, it was found that thefluorescene intensity of TPE compounds was stronger than that of TPE-Fccompounds.
TG study showed that all the TPE-Fc compounds and TPE compoundswere better thermally stable below240℃.In addition，the thermal stability ofTPE-Fc compounds increased by about60℃than that of TPE compounds.
The quantum chemical calculations at B3LYP/6-31G**levels of theory have been performed on TPE and TPE-Fc. The optimized geometries of TPEand TPE-Fc in the electronic ground state were obtained. TPE and TPE-Fcwere found to be non-planar. The electron cloud delocalization and energyvalues of the highest occupied molecular orbital (HOMO) and lowestunoccupied molecular orbital (LUMO) of TPE and TPE-Fc, were obtainedand found that that electron transfer occurred from the HOMO to the LUMOin TPE-Fc. Based on the calculated electronic properties and geometries, theelectrostatic first hyperpolarizability βμ were calculated using theDFT/B3LYP method and found that βμ (TPE)<βμ (TPE-Fc).
以所合成的含有羟基的三苯乙烯化合物为原料，通过与氯苯芳茂铁盐的亲核取代反应，合成了五种含芳茂铁基团的三苯乙烯化合物，分别为：(η~5-环戊二烯)[η~6-1-(1-苯基-2-甲基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-1)、(η~5-环戊二烯)[η~6-1-(1，2-二苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-2)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-氯苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-3)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-苯氧基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-4)、(η~5-环戊二烯)[η~6-1-(1-苯基-2-苯硫基苯基)丁烯氧基苯]铁六氟磷酸盐(TPE-Fc-5)，该五种茂铁盐均未见文献报道。
所制备的含羟基的三苯乙烯化合物和含芳茂铁基团的三苯乙烯化合物均经过IR、LC-MS、~1H-NMR和~(13)C-NMR进行表征，确定了物质结构。
对所合成的两类烯烃通过紫外可见吸收光谱研究发现,含芳茂铁基团的三苯乙烯化合物与含羟基的三苯乙烯化合物在200-350nm具有较强的吸收，取代基影响较小。引入茂铁盐后，在400-500nm产生由d-d跃迁产生的弱吸收。考查了溶剂极性对所合成的两类烯烃的紫外吸收光谱的影响，发现吸收峰随着极性的增大，峰型变窄，峰位红移。系统考查了所制备的两种烯烃在可见光下的光稳定性，含有羟基的三苯乙烯化合物具有很好的光稳定性，含有芳茂铁基团的三苯乙烯化合物随着光照时间的增长会有一定的光解。考查了所制备的两类三苯乙烯化合物的荧光发射光谱，研究发现在三苯乙烯化合物中引入芳茂铁基团，使三苯乙烯化合物的荧光减弱，荧光量子效率降低。
所制备的含芳茂铁基团的三苯乙烯化合物和含羟基的三苯乙烯化合物经热重研究发现，在240℃以下具有良好的热稳定性。此外发现引入芳茂铁基团后，TPE-Fc化合物比TPE化合物的热稳定性提高了60℃左右。
通过密度泛函理论(DTF)在B3LYP/6-31G**水平上，对所合成的三苯乙烯化合物进行了分子结构优化，发现三苯乙烯化合物在结构上不是平面型化合物，苯环和苯环之间具有一定的二面角；通过计算获得了前线轨道的能级及其电荷分布，发现同羟基三苯乙烯化合物相比，带有茂铁基的三苯乙烯化合物的HOMO轨道和LUMO轨道的能级差变小，并从HOMO轨道到LUMO轨道有明显的电荷转移；通过最优结构偶极距参数，计算了分子的一阶超极化率，发现在三苯乙烯化合物中引入茂铁基使分子的一阶超级化率显著提高。
Aryl ketone and4-hydroxyl dibenzophenone as raw materials, fivehydroxyl substituted triphenyl butene compounds were synthesized by theMcMurry coupling reaction, including1-(4-hydroxyphenyl)-2-(4-methylphenyl)-1-phenylbutylene(TPE-1),1,2-diphenyl-1-(4-hydroxyphenyl)butylene (TPE-2),2-(4-chlorophenyl)-1-(4-hydroxyphenyl)-1-phenylbutylenes(TPE-3),1-(4-hydroxyphenyl)-1-phenyl-2-(4-phenyloxyphenyl)but-ylenes(TPE-4),1-(4-hydroxyphenyl)-1-phenyl-2-(4-thiophenolphenyl)butyl-enes(TPE-5). Among the five hydroxyl substituted triphenyl butenecompounds, TPE-4and TPE-5were not reported.
Five triphenyl butane derivatives containing a cyclopentadienyl iron unitwere synthesized vis the SNAr reaction, including(η~5-Cyclopentadienyl)(η~6-1-(2-(4-methylphenyl)-1-phenyl)butyleneoxylphenyl] Fe hexafluorophosphate(TPE-Fc-1),[(η~5-Cyclopentadienyl)-Fe-(η~6-1-(1,2-diphenyl)butyleneoxylphenyl] Fe hexafluorophosphate(PHB-Fc-2),(η~5-Cycl-opentadienyl)(η~6-1-(2-(4-chlorophenyl)-1-phenyl)butyleneoxylphenyl] Fe he-xafluorophosphate(TPE-Fc-3),(η~5-Cyclopentadienyl)(η~6-1-(2-(4-phenylxyph- enyl)-1-phenyl)butyleneoxylphenyl] Fe hexafluorophosphate(TPE-Fc-4),(η~5-Cyclopentadienyl)(η~6-1-(2-(4-phenolthiophenyl)-1-phenyl) butyleneoxylphenyl] Fe hexafluorophosphate (TPE-Fc-5), all the compounds were not reportedbefore.
The structure of the target compounds were identified by IR, LC-MC,~1H-NMR and~(13)C-NMR.
The UV-Vis absorption properties of the target compounds were studied.TPE-Fc and TPE all show stronger absorption in200-350nm, and TPE-Fccompounds possesses weak absorption between400and500nm owing to thed-d transition of the cyclopentadienyl iron unit. The difference of substitutedgroup in TPE-Fc and TPE has little effect on the UV-Vis absorption. UV-Visabsorption of TPE-Fcs in various solvents with different polarities wereinvestigated and found that all showed positive solvatochromism(bathochromic shift) upon the increase in solvent polarity. The study ofphotolysis found that TPE is photostable, but TPE-Fc can carry out photolysis.From the fluorescence spectra of the target compounds, it was found that thefluorescene intensity of TPE compounds was stronger than that of TPE-Fccompounds.
TG study showed that all the TPE-Fc compounds and TPE compoundswere better thermally stable below240℃.In addition，the thermal stability ofTPE-Fc compounds increased by about60℃than that of TPE compounds.
The quantum chemical calculations at B3LYP/6-31G**levels of theory have been performed on TPE and TPE-Fc. The optimized geometries of TPEand TPE-Fc in the electronic ground state were obtained. TPE and TPE-Fcwere found to be non-planar. The electron cloud delocalization and energyvalues of the highest occupied molecular orbital (HOMO) and lowestunoccupied molecular orbital (LUMO) of TPE and TPE-Fc, were obtainedand found that that electron transfer occurred from the HOMO to the LUMOin TPE-Fc. Based on the calculated electronic properties and geometries, theelectrostatic first hyperpolarizability βμ were calculated using theDFT/B3LYP method and found that βμ (TPE)<βμ (TPE-Fc).
引文
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