【作者】 王栋；

【导师】 师同顺；

【作者基本信息】 吉林大学 ， 无机化学， 2009， 博士

【摘要】 (1)我们合成了基于卟啉和芴的树枝状分子发光材料配体及其金属锌的配合物,通过对苯二酚醚的Blanc-Sommelet反应、与芴缩合、三氟化硼乙醚催化下与吡咯成功缩合出目标配体,然后在氯仿中与乙酸锌反应制得锌配合物。用元素分析,质谱,核磁共振氢谱,核磁共振碳谱,紫外光谱等对其进行了结构表征,证明是我们所要合成的目标化合物。(2)对合成的目标化合物P和ZnP进行荧光,电化学和电致发光性质的研究。荧光光谱显示相对于TPP而言P和ZnP有很强的荧光强度,荧光量子产率也很高,P的量子产率是0.19大概是TPP(0.11)的两倍,ZnP的量子产率是0.29大概是TPP(0.11)的三倍。将P以1%的掺杂浓度掺杂到PVK中制备的单层电致发光器件研究显示橙红色的发光,最大亮度是109 cd/m~2,发光效率是0.036 cd/A,相对于TPP,P显示了一个更好的发光性能。(3)通过NBS,Wittig等反应设计合成了基于二茂铁的树枝状卟啉功能材料,并用紫外光谱和核磁共振氢谱对其进行表征,最后讨论了其合成条件和方法。(4)合成了由乙基香兰素和5-(4-氨基)苯基-10,15,20-三苯基卟啉缩合而成的卟啉Schiff Base,然后通过用元素分析,质谱,核磁共振氢谱,紫外光谱等对其进行表征,分析并讨论了其分离提纯的优化条件。(5)合成了以癸烷为桥的苯环上带有甲氧基、氯和氢三种取代基的卟啉-烟酸二元化合物,并讨论了取代基效应对所合成的卟啉-烟酸二元化合物的荧光,电化学和激光拉曼光谱的影响及变化规律。更多还原

【Abstract】 Porphyrin and its derivatives were excellent organic semiconductor materials and they were received considerable attention in recent years.They were found to exhibit interesting electronic and optical properties.In this paper,the unreported porphyrin P and its zinc complex ZnP by bonding the 9 position of fluorene throughπ-conjugation were designed,synthesized and characterized by EA,MS,UV-Vis,¹H NMR,¹³C NMR,and we studied their properties of fluorescence,redox and electroluminescence.We researched and discussed synthesis conditions of functional material based on porphyrin and ferrocene.The synthesis and characterization of the porphyrin-Schiff base are described.The porphyrin-Schiff base via the condensation of 5-（4-aminophenyl）-10,15,20-triphenylporphyiin using ethylvanillin has synthesized.The porphyrin-Schiff base prepared in this study was unstable during the purification process.After the structural character of the porphyrin-Schiff base is analyzed,and the condition of the separation is changed,the porphyrin-Schiff base has been obtained successfully,and the mechanism of the decomposition has been analyzed and confirmed.Porphyrin nicotinic acid binary compounds with different substituents were synthesized.Electrochemical and spectroscopic properties of the porphyrin nicotinic acid binary compounds with different substituents in porphine rings were studied by using cyclic voltammetry,fluorescence spectra and Resonance Raman spectra.Our work includes the following aspects:（1） The synthesis ofπ-conjugated porphyrins（P） based on fluorene described here involves the preparation of aldehyde precursors by a multistep procedure via blanc-sommelet reaction of 1,4-dibutoxy benzene and condensation with fluorene.Successive condensation with pyrrole is performed under Lindsey condition:acid catalysis at high dilution followed by addition of oxidant.The zinc（Ⅱ） porphyrin（ZnP） complex was synthesized in the mixture of chloroform and ethanol contained zinc acetate. P and ZnP were characterized by EA,MS,UV-Vis,¹H NMR,¹³C NMR.The UV-vis absorption spectra of the porphyrin（P）,zinc（Ⅱ） porphyrin（ZnP） and tetraphenylporphyrin（TPP） in the dilute dichloromethane(10^-6 M) reveal typical features of porphyrin chromophore with Soret and Q-bands.In comparison with TPP,the Soret bands of P and ZnP exhibit markedly red-shift（about 14 nm）,and the Q-bands also reveal slight red-shift.Scheme.Synthetic route of Electroluminescentπ-Conjugated Dendrimers Derived from Porphyrin and Fluorene（2） We studied the properties of P and ZnP about fluorescence,redox and electroluminescence.The fluorescence spectra of the P,ZnP and TPP exhibit that the P has an intense red emission peak at around 652 nm with a shoulder at 712 nm,the ZnP intense red emission peak at around 599 nm with a shoulder at 646 nm,while the TPP shows two relatively weak emission peaks at around 649 nm and 710 nm.The fluorescence quantum yields（φ_F） of the P and ZnP are 0.19 and 0.29,respectively,which are much higher than that of many porphyrin derivatives.In the EL spectra,the single-layer devices with 1 wt%（P） doping concentration show salmon pink color with the CIE coordinate of（0.51,0.38）.The J-V-B curve of device using P exhibits a maximum luminance of 109.3 cd m^-2 at 20 V and a maximum luminance efficiency of 0.036 cd A^-1 at 19 V.Device using P exhibits higher device performance than that based on TPP.（3） We designed and synthesized functional material based on porphyrin and ferrocene.Synthesis of functional material based on porphyrin and ferrocene involves the preparation of aldehyde precursors by a multistep procedure via NBS reaction and Wittig reaction.The compounds were characterized by UV-vis and ¹H NMR spectra,and we analyzed and discussed its synthesis conditions.Scheme.Synthetic route of functional Dendrimer Derived from Porphyrin and Ferrocene（4） The porphyrin-Schiff base via the condensation of 5-（4-aminophenyl）-10,15, 20-triphenylporphyiin using ethylvanillin has been synthesized.The porphyrin-Schiff base prepared in this study was unstable during the purification process.After the structural character of the porphyrin-Schiff base is analyzed,and the condition of the separation is changed,the porphyrin-Schiff base has been obtained successfully,and the mechanism of the decomposition has been analyzed and confirmed.Scheme.Synthetic route of Porphyrin-Schiff Base（5） We found the synthesis and properties of the porphyrin linked with nicacid are Worth studying in depth.It’s possible to realize the dual activity of porphyrin and nicacid.Furthermore,it can potentially be used as a building block of supermolecule assembly via noncovalently weak interactions including coordination bonding and/or hydrogen bonding of the N,O atoms of nicotinic acid.Porphyrin nicotinic acid binary compounds with different substituents were synthesized.Fluorescence,Raman spectra and electrochemical behavior of these compounds were investigated.The effects of substituents on their properties were also analyzed.The results show that the different substituents of porphyrin ring influence the intensity and quantum yield of fluorescence,namely,the methoxy groups increase the intensity and quantum yield of the porphyrin and the chloric groups decrease them.The redox behavior shows that the electron-donating groups（CH30） make the electron density of the porphyrin ring greater,therefore,it is easy to oxidize,and the electron-withdrawing groups（Cl） make it easy to reduce.For the Raman spectra,the substituent effects are slight.更多还原