咔咯配合物的合成及性质研究
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摘要
咔咯(corrole)是一类由四个吡咯共轭相连形成的大环化合物。它们的分子结构和卟啉相似,但又具有一定的特殊性。因此它们具有比较特殊的光化学、电化学、光物理和光生物性质,在功能材料、生物医药、光催化及电催化剂等领域都具有广泛的应用前景。
本论文介绍了咔咯及其金属配合物的结构、性质、主要的合成方法及其研究和应用进展。采用改进的Lindsey法以乙醇和水混合溶剂为介质合成了三苯基咔咯1,三(对氯苯基)咔咯2,三(邻硝基苯基)咔咯3,三(间硝基苯基)咔咯4和三(对硝基苯基)咔咯5等五种咔咯化合物,用元素分析、红外、紫外—可见、核磁共振图谱以及电化学方法对化合物进行了表征。
详细测定了在十一种不同的非水溶剂以及两种浓强酸溶液中咔咯化合物的紫外—可见光谱,研究了溶剂的酸碱性对化合物的光谱以及存在形式的影响。研究结果表明在浓乙酸、0.1mol/L硫酸或高氯酸的二氯甲烷溶液中,得到的是质子化的咔咯化合物。在碱性溶剂中生成的是失去质子的产物。在浓的强酸溶液中,已经得到一个质子的咔咯分子会开环分解。根据在苯腈中用三氟乙酸滴定咔咯化合物时光谱的变化,测定并计算了咔咯化合物的质子化常数。
研究了环境光照对咔咯化合物紫外—可见光谱的影响,发现咔咯化合物1和2的CH_2Cl_2溶液在自然光照射下的紫外—可见光谱吸收强度会有明显的降低,说明在给定的实验条件下这两个化合物不稳定容易发生开环分解反应。但是,在同样的实验条件下光照对分子中具有硝基取代基的化合物3、4、5的光谱只有很小的影响,说明硝基的存在可以使这类化合物更稳定。
测定了咔咯化合物在二氯甲烷和DMF溶剂中中的荧光光谱,实验表明所测定的咔咯化合物都具有较好的荧光性质。另外,还用循环伏安法测定了咔咯化合物在含有0.1 mol/L高氯酸四正丁基铵的DMF溶液中的电化学性质,发现在给定的实验条件下所研究的化合物都可以发生两到三级电还原反应。
Corroles are a class of macrocycle compounds containing four conjugated pyrroles.These compounds have similar molecular structures to porphyrins,but also have certain particularities as compared to the corresponding porphyrins.Therefore, the corroles have unique properties of photochemistry,electrochemistry,photophysics and photobiology,and have a lot of potential applications in the field of functional materials,biomedicine,phtocatalysts or electrocatalysts.
In this thesis,the structures,properties,the main synthetic methods and the progress of research and applications for the corrole and metallocorroles were introduced.Five corroles,i.e.triphenylcorrole 1,tri-4-chlorophenylcorrole 2, tri-2-nitrophenylcorrole 3,tri-3-nitrophenylcorrole 4 and tri-4-nitrophenylcorrole 5 were synthesized by an improved Lindsey method in the mixture of ethanol and H_2O. The sythesized corroles were characterized by elemental analysis,FT-IR,UV-Vis,1~H NMR spectroscopies and electrochemistry.
UV-visible spectra of the corroles were measured in eleven different nonaqueous solvents as well as in two solutions of neat concentrated acid.The effect of solvent acidity or basicity on the spectra and existing forms of the corroles was discussed. The results indicate that the products are the protonated corroles in concentrated acetic acid or in CH_2Cl_2 containing 0.10 mol/L H_2SO_4 or HClO_4.The deprotonated corroles were formed in basic solvents.The protonated corroles may decompose due to the conjugated macrocycle being broken in the presence of concentrated strong acids.The protonation constants(logK) of corroles were determined based on the spectral changes obtained during a titration with TFA in PhCN.
The effect of environmental illumination on the UV-visible spectra of corroles have been studied.The spectra of compounds 1 and 2 decreased in intensity under the natrual light in CH_2Cl_2 indicating that both 1 and 2 are not stable and could easily occur the reactions of decomposion and breaking macrocycle under the given experimental conditions.However,environmental illumination only has a weak effect on the spectra of the compounds 3,4 and 5 with nitro substituents under the same experimental conditions.The results indicate that the nitro substituents may lead to corroles more stable.
The fluorescence spectra of the corroles were measured in CH_2Cl_2 and DMF and the results indicate that all investigated corroles possess good fluorescence properties. In addition,the electrochemical properties of the corroles were also studied by cyclic voltammetry in DMF containing 0.1 mol/L tetra-n-butylammonium perchlorate.Two or three reductions can be observed for these corroles under the given experimental conditions.
本论文介绍了咔咯及其金属配合物的结构、性质、主要的合成方法及其研究和应用进展。采用改进的Lindsey法以乙醇和水混合溶剂为介质合成了三苯基咔咯1,三(对氯苯基)咔咯2,三(邻硝基苯基)咔咯3,三(间硝基苯基)咔咯4和三(对硝基苯基)咔咯5等五种咔咯化合物,用元素分析、红外、紫外—可见、核磁共振图谱以及电化学方法对化合物进行了表征。
详细测定了在十一种不同的非水溶剂以及两种浓强酸溶液中咔咯化合物的紫外—可见光谱,研究了溶剂的酸碱性对化合物的光谱以及存在形式的影响。研究结果表明在浓乙酸、0.1mol/L硫酸或高氯酸的二氯甲烷溶液中,得到的是质子化的咔咯化合物。在碱性溶剂中生成的是失去质子的产物。在浓的强酸溶液中,已经得到一个质子的咔咯分子会开环分解。根据在苯腈中用三氟乙酸滴定咔咯化合物时光谱的变化,测定并计算了咔咯化合物的质子化常数。
研究了环境光照对咔咯化合物紫外—可见光谱的影响,发现咔咯化合物1和2的CH_2Cl_2溶液在自然光照射下的紫外—可见光谱吸收强度会有明显的降低,说明在给定的实验条件下这两个化合物不稳定容易发生开环分解反应。但是,在同样的实验条件下光照对分子中具有硝基取代基的化合物3、4、5的光谱只有很小的影响,说明硝基的存在可以使这类化合物更稳定。
测定了咔咯化合物在二氯甲烷和DMF溶剂中中的荧光光谱,实验表明所测定的咔咯化合物都具有较好的荧光性质。另外,还用循环伏安法测定了咔咯化合物在含有0.1 mol/L高氯酸四正丁基铵的DMF溶液中的电化学性质,发现在给定的实验条件下所研究的化合物都可以发生两到三级电还原反应。
Corroles are a class of macrocycle compounds containing four conjugated pyrroles.These compounds have similar molecular structures to porphyrins,but also have certain particularities as compared to the corresponding porphyrins.Therefore, the corroles have unique properties of photochemistry,electrochemistry,photophysics and photobiology,and have a lot of potential applications in the field of functional materials,biomedicine,phtocatalysts or electrocatalysts.
In this thesis,the structures,properties,the main synthetic methods and the progress of research and applications for the corrole and metallocorroles were introduced.Five corroles,i.e.triphenylcorrole 1,tri-4-chlorophenylcorrole 2, tri-2-nitrophenylcorrole 3,tri-3-nitrophenylcorrole 4 and tri-4-nitrophenylcorrole 5 were synthesized by an improved Lindsey method in the mixture of ethanol and H_2O. The sythesized corroles were characterized by elemental analysis,FT-IR,UV-Vis,1~H NMR spectroscopies and electrochemistry.
UV-visible spectra of the corroles were measured in eleven different nonaqueous solvents as well as in two solutions of neat concentrated acid.The effect of solvent acidity or basicity on the spectra and existing forms of the corroles was discussed. The results indicate that the products are the protonated corroles in concentrated acetic acid or in CH_2Cl_2 containing 0.10 mol/L H_2SO_4 or HClO_4.The deprotonated corroles were formed in basic solvents.The protonated corroles may decompose due to the conjugated macrocycle being broken in the presence of concentrated strong acids.The protonation constants(logK) of corroles were determined based on the spectral changes obtained during a titration with TFA in PhCN.
The effect of environmental illumination on the UV-visible spectra of corroles have been studied.The spectra of compounds 1 and 2 decreased in intensity under the natrual light in CH_2Cl_2 indicating that both 1 and 2 are not stable and could easily occur the reactions of decomposion and breaking macrocycle under the given experimental conditions.However,environmental illumination only has a weak effect on the spectra of the compounds 3,4 and 5 with nitro substituents under the same experimental conditions.The results indicate that the nitro substituents may lead to corroles more stable.
The fluorescence spectra of the corroles were measured in CH_2Cl_2 and DMF and the results indicate that all investigated corroles possess good fluorescence properties. In addition,the electrochemical properties of the corroles were also studied by cyclic voltammetry in DMF containing 0.1 mol/L tetra-n-butylammonium perchlorate.Two or three reductions can be observed for these corroles under the given experimental conditions.
引文
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